技术领域technical field
本发明涉及一种制备加氢催化剂的方法，特别是用于含分子筛的加氢催化剂的制备方法。The invention relates to a method for preparing a hydrogenation catalyst, in particular to a method for preparing a hydrogenation catalyst containing molecular sieves.
背景技术Background technique
世界经济的迅速发展和原油逐步变差，使得市场对轻质油品和化工原料的需求量逐年增加。加氢裂化技术是原油二次加工、重油轻质化的重要手段之一得到了日益广泛的应用。The rapid development of the world economy and the gradual deterioration of crude oil make the market demand for light oil products and chemical raw materials increase year by year. Hydrocracking technology is one of the important means for the secondary processing of crude oil and the lightening of heavy oil, and it has been increasingly widely used.
加氢裂化技术的关键加氢裂化催化剂。加氢裂化催化剂是一种双功能催化剂，其裂解活性和加氢活性是由催化剂中的酸性组分和加氢活性组分分别来提供的。催化剂中的酸性组分一般是由催化剂中所含的分子筛和/或无定形硅铝来提供的。分子筛具有较强的酸性，是催化剂中的主要裂解组分，具有反应温度低，活性强等特点。无定形硅铝催化剂反应温度较高，但是反应较为缓和，中油选择性好。分子筛同无定形硅铝和分子筛组合使用是加氢裂化催化剂发展的主要方向。而且通过分子筛和无定形硅铝所制得的催化剂具有良好的活性、选择性及稳定性，适合于长周期运转。The key hydrocracking catalyst of hydrocracking technology. The hydrocracking catalyst is a dual-functional catalyst, and its cracking activity and hydrogenation activity are respectively provided by the acidic component and the hydrogenation active component in the catalyst. The acidic component of the catalyst is generally provided by molecular sieves and/or amorphous silica alumina contained in the catalyst. Molecular sieve has strong acidity and is the main cracking component in the catalyst. It has the characteristics of low reaction temperature and strong activity. The reaction temperature of amorphous silica-alumina catalyst is relatively high, but the reaction is relatively moderate, and the selectivity of medium oil is good. Combination of molecular sieves with amorphous silica-alumina and molecular sieves is the main direction for the development of hydrocracking catalysts. Moreover, the catalyst prepared by molecular sieve and amorphous silica-alumina has good activity, selectivity and stability, and is suitable for long-term operation.
载体中的分子筛与无定形硅铝之间的结合度和分散度与其反应性能之间有着密不可分的关系，分散性好则载体的酸中心分布均匀，反应物料在催化剂中反应较为均匀；在很大程度上影响催化剂的活性以及对各种目的产品的选择性。如何解决分子筛和无定形硅铝载体之间的分散性是制备具有良好反应性能催化剂的关键。There is an inseparable relationship between the degree of bonding and dispersion between the molecular sieve and the amorphous silica-alumina in the carrier and its reaction performance. If the dispersion is good, the acid centers of the carrier will be evenly distributed, and the reaction materials will react more uniformly in the catalyst; To a large extent, it affects the activity of the catalyst and the selectivity to various target products. How to solve the dispersion between molecular sieves and amorphous silica-alumina supports is the key to preparing catalysts with good reactivity.
CN201010197869.1、CN200810117102.6、CN00105235.7等专利中公开的加氢裂化催化剂都是将分子筛、氧化铝等单一的原料经过机械混合后制备的。该方法所制备的催化剂会因各种原料混合不均匀，影响各组分性能的发挥。The hydrocracking catalysts disclosed in patents such as CN201010197869.1, CN200810117102.6, and CN00105235.7 are prepared by mechanically mixing single raw materials such as molecular sieve and alumina. The catalyst prepared by this method will affect the performance of each component due to uneven mixing of various raw materials.
CN1060976A公开了一种含无定形氧化铝的超稳Y型沸石的制备方法。该方法是向硫酸铝溶液中加入氨水调节pH值为3.5～7.5，然后加入NaY沸石或HNaY沸石，混合均匀，再按水热法制备USY沸石过程进行铵离子交换和水热处理等后续处理，得到含无定形氧化铝的超稳Y型沸石。该方法是在氧化铝成胶后，加入沸石原料，再按常规方法改性所得的复合材料。该方法存在无定形氧化铝容易出现团聚现象，使无定形氧化铝在分子筛上的分布不均匀，甚至堵塞分子筛的孔道，使催化剂的比表面积和孔容大幅度减少，而且分子筛与氧化铝孔道的通畅性较差，影响催化剂的性能。该方法通过NaY沸石同无定形氧化铝复合后再进行水热处理及铵交换过程，加大了处理量，降低了处理的效率，处理过程中无定形氧化铝会一起被处理，容易对氧化铝产生不良效应。CN1060976A discloses a preparation method of ultra-stable Y-type zeolite containing amorphous alumina. The method is to add ammonia water to the aluminum sulfate solution to adjust the pH value to 3.5-7.5, then add NaY zeolite or HNaY zeolite, mix evenly, and then carry out follow-up treatments such as ammonium ion exchange and hydrothermal treatment according to the process of preparing USY zeolite by the hydrothermal method to obtain Ultrastable Y-type zeolite with amorphous alumina. The method is to add the zeolite raw material after the alumina is gelled, and then modify the obtained composite material according to the conventional method. In this method, amorphous alumina is prone to agglomeration, which makes the distribution of amorphous alumina on the molecular sieve uneven, and even blocks the pores of the molecular sieve, greatly reducing the specific surface area and pore volume of the catalyst, and the molecular sieve and alumina pores. Poor patency will affect the performance of the catalyst. In this method, hydrothermal treatment and ammonium exchange process are carried out after NaY zeolite is combined with amorphous alumina, which increases the treatment capacity and reduces the treatment efficiency. During the treatment process, amorphous alumina will be treated together, which is easy to produce adverse effects.
CN200610134152.6公开了一种加氢催化剂的制备方法，该方法是采用一种含有分子筛和无定形硅铝的载体材料，采用浸渍法或共沉淀法制备最终催化剂。其中载体材料是在无定形硅铝成胶过程中直接加入分子筛的方法制备的。该方法中无定形硅铝容易出现团聚现象，还容易进入对方的孔道或堵塞分子筛的孔口，影响无定形硅铝在分子筛上的分布，分子筛与无定形硅铝孔道的贯通性较差，使催化剂的比表面积和孔容减少，催化剂活性金属分布不均匀，影响催化剂的性能。CN200610134152.6 discloses a method for preparing a hydrogenation catalyst. The method uses a carrier material containing molecular sieve and amorphous silica-alumina, and prepares the final catalyst by impregnation or co-precipitation. The carrier material is prepared by directly adding molecular sieves in the process of forming amorphous silica-alumina colloid. In this method, amorphous silicon-alumina is prone to agglomeration, and it is also easy to enter the pores of the other party or block the orifice of the molecular sieve, which affects the distribution of amorphous silicon-alumina on the molecular sieve, and the connectivity between molecular sieve and amorphous silicon-alumina channels is poor. The specific surface area and pore volume of the catalyst are reduced, and the distribution of the active metal of the catalyst is uneven, which affects the performance of the catalyst.
发明内容Contents of the invention
为了克服现有技术的不足，本发明提供了一种制备加氢催化剂的方法。由该方法制备的催化剂将分子筛和无定形硅铝有机的结合在一起，具有良好的结合度及分散度，可以避免分子筛和和大孔无定形硅铝间出现团聚甚至堵塞现象，提高催化剂的使用性能。In order to overcome the deficiencies of the prior art, the invention provides a method for preparing a hydrogenation catalyst. The catalyst prepared by this method organically combines the molecular sieve and the amorphous silica-alumina, has a good degree of combination and dispersion, can avoid agglomeration or even blockage between the molecular sieve and the large-pore amorphous silica-alumina, and improves the use of the catalyst. performance.
本发明制备加氢催化剂的方法，包括：制备含有分子筛和无定形硅铝的催化剂载体材料，采用浸渍法或共沉淀法引入加氢活性组分，得到最终加氢催化剂，其中催化剂载体材料的制备过程包括：The method for preparing a hydrogenation catalyst of the present invention includes: preparing a catalyst carrier material containing molecular sieves and amorphous silica-alumina, introducing a hydrogenation active component by impregnation or co-precipitation to obtain a final hydrogenation catalyst, wherein the preparation of the catalyst carrier material The process includes:
(1) 将分子筛与有机胺类混合，其中有机胺类的加入量占分子筛重量的1wt%~40wt%；(1) mixing molecular sieves with organic amines, wherein the addition of organic amines accounts for 1wt% to 40wt% of the molecular sieve weight;
(2) 在无定形硅铝成胶过程中加入步骤（1）得到的混合物以及有机物，以最终载体材料的重量为基准，分子筛加入量为5wt%~90wt%，有机物的加入量为1wt%~50wt%，所述的有机物为含两个或者两个以上羟基的有机醇类、含有两个或两个以上羧基的有机酸类中的一种或多种；(2) Add the mixture obtained in step (1) and organic matter in the process of forming amorphous silica-alumina gel. Based on the weight of the final carrier material, the amount of molecular sieve added is 5wt%~90wt%, and the amount of organic matter added is 1wt%~ 50wt%, the organic matter is one or more of organic alcohols containing two or more hydroxyl groups and organic acids containing two or more carboxyl groups;
(3) 在步骤（2）所述的无定形硅铝成胶结束后进行老化，然后经过滤、洗涤、干燥，得到催化剂载体干胶粉。(3) Aging is carried out after the amorphous silica-alumina colloidal formation described in step (2), and then filtered, washed and dried to obtain dry rubber powder of the catalyst carrier.
本发明步骤（1）中，所述的有机胺类为碳原子数小于20个的脂肪胺、芳香胺、醇胺中的一种或多种。较适合的为含有链状的胺类，优选为含有2~10个碳原子数的脂肪胺类中的一种或多种。例如：丙胺、叔丁胺；癸胺、二甲胺、二丙胺、丁胺、己胺、乙胺、2-乙基己胺、二乙胺、二异丙胺、己二胺、1,2-二甲基丙胺、仲丁胺、1,5-二甲基己胺、乙二胺、1,2-丙二胺、1,4-丁二胺、一乙醇胺、二乙醇胺、三乙醇胺、3-丙醇胺、一异丙醇胺、二异丙醇胺、三异丙醇胺、苯胺中的一种或多种。有机胺类与分子筛混合，可以将有机胺类直接加入分子筛中，也可以将有机胺类溶于溶剂中再加入分子筛中，其中的溶剂为水、低碳醇（即碳原子数为1~5的一元醇中的一种或多种）中的一种或多种。若有机胺类的加入量较大，需要过滤并干燥后再进行步骤（2）。In step (1) of the present invention, the organic amines are one or more of aliphatic amines, aromatic amines, and alcohol amines with less than 20 carbon atoms. It is more suitable to contain chain amines, preferably one or more of aliphatic amines containing 2 to 10 carbon atoms. For example: propylamine, tert-butylamine; decylamine, dimethylamine, dipropylamine, butylamine, hexylamine, ethylamine, 2-ethylhexylamine, diethylamine, diisopropylamine, hexamethylenediamine, 1,2-dimethylamine Propylamine, butylamine, 1,5-dimethylhexylamine, ethylenediamine, 1,2-propylenediamine, 1,4-butylenediamine, monoethanolamine, diethanolamine, triethanolamine, 3-propanol One or more of amine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, aniline. Organic amines are mixed with molecular sieves. Organic amines can be directly added to molecular sieves, or organic amines can be dissolved in solvents and then added to molecular sieves. The solvents are water and low-carbon alcohols (that is, the number of carbon atoms is 1~5 One or more of monohydric alcohols). If the amount of organic amines added is large, it needs to be filtered and dried before proceeding to step (2).
本发明步骤（2）中所述的无定形硅铝成胶过程可以按本领域技术人员熟知的过程进行。无定形硅铝成胶过程一般为酸性物料和碱性物料的中和反应过程，成胶过程一般采用两种物料并流成胶操作方式，或一种物料放置在成胶罐中另一种物料连续加入成胶的操作方式。成胶物料一般包括铝源（Al2(SO4)3、AlCl3、Al(NO3)3和NaAlO2等中的一种或几种）、硅源（水玻璃、硅溶胶和有机含硅化合物等中的一种或几种）、沉淀剂（NaOH、NH4OH或CO2等），根据成胶过程的不同选择使用，常规的操作方式主要有：（1）酸性铝盐（Al2(SO4)3、AlCl3、Al(NO3)3）与碱性铝盐（NaAlO2）或碱性沉淀剂（NaOH、NH4OH）中和成胶，（2）碱性铝盐（NaAlO2）与酸性沉淀剂（CO2）中和成胶。硅源一般在成胶过程中引入成胶罐，也可以与铝源或沉淀剂混合后再中和成胶，如水玻璃加入碱性铝盐或碱性沉淀剂中进行中和成胶，硅溶胶加入酸性铝盐中进行中和成胶等。硅源也可以加入铝源沉淀后物料中。也可以将上述方式两种或两种以上结合使用。上述方法均是本领域技术人员所熟知的。所述的成胶过程一般在室温~85℃下进行，较适合为40~80℃，优选为50~70℃。所述的成胶过程一般在一定的pH值条件下进行，典型的pH为6.0~10.0，较适合为7.0~9.5，优选为7.5~9.0。步骤（3）所述的老化，条件如下：pH为6.0~10.0，优选为7.0~9.5，老化时间0.25~8小时，较适合在0.5~5小时，优选为1~3小时，老化温度为室温~85℃，优选为40~80℃。老化时的温度和pH与中和时的温度和pH最好相同。The amorphous silica-alumina colloidal process described in step (2) of the present invention can be carried out according to processes well known to those skilled in the art. The gelling process of amorphous silica-alumina is generally the neutralization reaction process of acidic materials and alkaline materials. The gelling process generally adopts the operation mode of co-flowing two materials into gels, or one material is placed in the gelation tank and the other material is placed in the gelling tank. The operation mode of adding gel continuously. Colloidal materials generally include aluminum source (one or more of Al2 (SO4 )3 , AlCl3 , Al(NO3 )3 and NaAlO2 , etc.), silicon source (water glass, silica sol and organic silicon-containing Compounds, etc.), precipitant (NaOH, NH4 OH or CO2 , etc.), can be selected and used according to different gelation processes, and the conventional operation methods mainly include: (1) acidic aluminum salt (Al2 (SO4 )3 , AlCl3 , Al(NO3 )3 ) and basic aluminum salt (NaAlO2 ) or basic precipitant (NaOH, NH4 OH) to form a gel, (2) basic aluminum salt ( NaAlO2 ) and acid precipitant (CO2 ) to form a gel. The silicon source is generally introduced into the gelation tank during the gelation process, and it can also be mixed with the aluminum source or a precipitant and then neutralized to form a gel. Add acidic aluminum salt for neutralization and gelation, etc. The silicon source can also be added to the material after the aluminum source is precipitated. It is also possible to combine two or more of the above methods. The above methods are well known to those skilled in the art. The gel forming process is generally carried out at room temperature~85°C, preferably at 40~80°C, preferably at 50~70°C. The gel forming process is generally carried out under a certain pH condition, the typical pH is 6.0-10.0, more suitable 7.0-9.5, preferably 7.5-9.0. The aging described in step (3), the conditions are as follows: the pH is 6.0~10.0, preferably 7.0~9.5, the aging time is 0.25~8 hours, more preferably 0.5~5 hours, preferably 1~3 hours, and the aging temperature is room temperature ~85°C, preferably 40~80°C. The temperature and pH during aging are preferably the same as those during neutralization.
本发明步骤（1）中，所述的分子筛为已知的任何一种或者几种分子筛，最好改性分子筛中的一种或者几种。在加氢催化剂中，常用的分子筛如Y型分子筛、β沸石、ZSM系列分子筛、SAPO系列分子筛、MCM系列分子筛等一种或几种，这些分子筛为本领域内技术人员所公知。为了获得希望的催化性能，各种分子筛可以进行适当的改性过程，改性方法为本领域技术人员所熟知的过程，如水热处理、酸处理、离子交换、各种溶剂处理等中的一种或多种方法改性。本发明步骤（1）中，所述的分子筛的加入状态可以是干粉状加入，也可以是以浆液形态加入。In step (1) of the present invention, the molecular sieve is any one or several known molecular sieves, preferably one or several modified molecular sieves. In the hydrogenation catalyst, one or several commonly used molecular sieves such as Y-type molecular sieves, zeolite beta, ZSM series molecular sieves, SAPO series molecular sieves, MCM series molecular sieves, etc., these molecular sieves are well known to those skilled in the art. In order to obtain the desired catalytic performance, various molecular sieves can be appropriately modified, and the modification method is a process well known to those skilled in the art, such as one or more of hydrothermal treatment, acid treatment, ion exchange, various solvent treatments, etc. Modified in many ways. In the step (1) of the present invention, the molecular sieve can be added in the form of dry powder or in the form of slurry.
本发明步骤（2）中，步骤（1）所得的混合物的引入方式采用下述方式的一种或几种组合：（1）在成胶中和反应过程中，将该混合物连续加入成胶罐中；（2）将该混合物先加入到成胶罐中，然后将制备无定形硅铝的酸性物料和碱性物料中和成胶；（3）将该混合物与成胶物料的一种或几种混合，然后成胶物料中和成胶。In step (2) of the present invention, the introduction method of the mixture obtained in step (1) adopts one or more combinations of the following methods: (1) During the gelation neutralization reaction process, the mixture is continuously added to the gelation tank (2) Add the mixture to the gel-forming tank first, and then neutralize the acidic material and alkaline material for preparing amorphous silica-alumina to form a gel; (3) Mix the mixture with one or more of the gel-forming materials Kind of mixing, and then the gel material is neutralized into gel.
本发明步骤（2）中所述的有机醇类为含两个或者两个以上羟基的有机化合物，其沸点高于成胶温度，一般在在100℃~350℃，优选是120℃以上，进一步优选150℃以上，例如二甘醇、三甘醇、四甘醇、丙二醇、丙三醇、1,4-丁二醇、丁三醇、2,2-二甲基-1,3丙二醇、二丙二醇、木糖醇、戊二醇、1,6-己二醇、己六醇中的一种或多种。所述的有机酸类为含两个或者两个以上羧基的有机化合物，其沸点高于成胶温度，一般在100℃~350℃，优选是120℃以上，进一步优选150℃以上，例如乙二酸（草酸）、丙二酸、柠檬酸、丁二酸、苹果酸、酒石酸、戊二酸、己二酸、庚二酸、辛二酸中的一种或多种。The organic alcohols described in step (2) of the present invention are organic compounds containing two or more hydroxyl groups, and their boiling point is higher than the gelling temperature, generally at 100°C to 350°C, preferably above 120°C, further Preferably above 150°C, such as diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, glycerin, 1,4-butanediol, butanetriol, 2,2-dimethyl-1,3 propanediol, di One or more of propylene glycol, xylitol, pentylene glycol, 1,6-hexanediol, and hexanediol. The organic acids mentioned above are organic compounds containing two or more carboxyl groups, and their boiling point is higher than the gelling temperature, generally between 100°C and 350°C, preferably above 120°C, more preferably above 150°C, for example, ethylene glycol One or more of acid (oxalic acid), malonic acid, citric acid, succinic acid, malic acid, tartaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid.
本发明步骤（2）中，所述有机物的加入方式可以选择下述方式的一种或几种组合：（1）在成胶初期预先加入到成胶罐中，（2）在成胶过程中滴加到成胶罐中，（3）同成胶原料的一种或几种混合，随物料加入成胶罐中。所述的有机物可以同步骤（1）所得的混合物一同加入，也可以单独加入。In the step (2) of the present invention, one or more combinations of the following methods can be selected for the addition of the organic matter: (1) pre-added to the gelation tank at the initial stage of gelation, (2) during the gelation process Add it dropwise into the glue-forming tank, (3) mix with one or several kinds of glue-forming raw materials, and add it into the glue-forming tank along with the materials. The organic matter can be added together with the mixture obtained in step (1), or can be added separately.
本发明步骤（3）中，所述的物料的洗涤方式是本领域技术人员所公知的，可以选择打浆洗涤、过滤时加水洗涤、低级醇类洗涤等方式，洗涤的温度应当在室温~90℃温度的范围内，优选50~70℃。所述的物料的洗涤一般在pH为1.0~9.0的范围内进行，优选pH为4.0~8.5。本发明步骤（3）中所述的物料在洗涤、过滤后应当不含或者含很少量的杂离子，杂离子包括Na+、Cl-、SO42-、NO3-、K+等中的一种或多种。In the step (3) of the present invention, the washing method of the materials is well known to those skilled in the art. You can choose beating washing, washing with water when filtering, washing with lower alcohols, etc. The washing temperature should be between room temperature and 90°C The range of temperature is preferably 50~70°C. The washing of the materials is generally carried out in the range of pH 1.0-9.0, preferably pH 4.0-8.5. The material described in the step (3) of the present invention should not contain or contain a small amount of miscellaneous ions after washing and filtering, and miscellaneous ions include Na+ , Cl- , SO42- , NO3- , K+ , etc. one or more of .
本发明步骤（3）中，所述的物料在洗涤、过滤后，滤饼进行干燥，干燥方式可以采用自然干燥、烘箱干燥、喷雾干燥、微波干燥或者红外干燥，一般干燥条件如下：在50~150℃下干燥1~15小时。In the step (3) of the present invention, after the materials are washed and filtered, the filter cake is dried. The drying method can be natural drying, oven drying, spray drying, microwave drying or infrared drying. The general drying conditions are as follows: Dry at 150°C for 1 to 15 hours.
本发明载体材料也可以根据需要添加其它助剂，如磷、硼、钛、锆等中的一种或多种。The carrier material of the present invention may also be added with other additives as required, such as one or more of phosphorus, boron, titanium, zirconium, etc.
本发明方法制备的载体干胶粉是一种制备催化剂载体的原料，经450~650℃焙烧2~10小时后，所得的性质如下：以焙烧后载体的重量为基准，分子筛的含量为5wt%~90wt%，无定形硅铝的含量在10 wt%~95wt%，无定形硅铝中，SiO2含量一般为10wt%~50wt%，焙烧后载体的性质如下：比表面积为200 ~1000m2/g，孔容为0.3 ~1.8cm3/g，红外酸量为0.1 ~2.0mmol/g。The carrier dry rubber powder prepared by the method of the present invention is a raw material for preparing a catalyst carrier. After roasting at 450-650 °C for 2-10 hours, the properties of the obtained are as follows: based on the weight of the carrier after roasting, the content of molecular sieve is 5wt%. ~90wt%, the content of amorphous silicon aluminum is 10 wt%~95wt%, in amorphous silicon aluminum, the content of SiO2 is generally 10wt%~50wt%, the properties of the carrier after calcination are as follows: the specific surface area is 200~1000m2 / g, the pore volume is 0.3 ~1.8cm3 /g, and the infrared acid content is 0.1 ~2.0mmol/g.
本发明方法中，加氢活性组分一般为第VIB族和第VIII族金属中一种或几种，如钼、钨、镍、钴等中的一种或几种，加氢活性组分在催化剂中的含量一般为5%~80%（以氧化物计，下同），适宜的含量为10%~50%，可以根据使用的要求具体确定。加氢活性组分的引入方法一般为浸渍法、共沉淀法等，具体引入方法是本领域技术人员熟知的内容。如采用浸渍法时，先将载体材料成型、干燥、焙烧，然后用含有活性加氢组分的溶液浸渍成型后的载体，再经干燥、焙烧，得到最终的加氢催化剂。采用共沉淀法时，将载体材料打浆，加氢活性金属沉淀到载体材料浆液中，然后经洗涤、成型、干燥、焙烧，得到最终加氢催化剂。上述催化剂制备过程及条件均是本领域技术人员熟知的。在载体成型过程中，还可以加入其它载体材料或助剂，如氧化硼、氧化钛、氧化锆等中的一种或几种。In the method of the present invention, the hydrogenation active component is generally one or more of Group VIB and Group VIII metals, such as one or more of molybdenum, tungsten, nickel, cobalt, etc., and the hydrogenation active component is The content in the catalyst is generally 5%~80% (calculated as oxides, the same below), and the suitable content is 10%~50%, which can be determined according to the requirements of use. The introduction method of the hydrogenation active component is generally the impregnation method, the co-precipitation method, etc., and the specific introduction method is well known to those skilled in the art. If the impregnation method is adopted, the carrier material is shaped, dried and calcined, and then the shaped carrier is impregnated with a solution containing active hydrogenation components, and then dried and calcined to obtain the final hydrogenation catalyst. When the co-precipitation method is used, the carrier material is beaten, and the hydrogenation active metal is precipitated into the carrier material slurry, and then washed, shaped, dried, and roasted to obtain the final hydrogenation catalyst. The above catalyst preparation process and conditions are well known to those skilled in the art. During the carrier molding process, other carrier materials or additives can also be added, such as one or more of boron oxide, titanium oxide, zirconium oxide, etc.
本发明加氢催化剂的制备过程中，分子筛预先与有机胺类混合，有机胺类会预先吸附到分子筛的孔道及孔口处，使分子筛的孔道结构预先得到保护， 这样可避免硅铝成胶过程中碎片进入孔道、堵塞孔口或者直接在孔道内成胶；同时有机胺类在硅铝成胶过程中具有对硅铝孔道的导向作用，并与硅铝成胶过程中加入的含羟基或羧基的有机物相配合，由于含羟基或羧基的有机物溶于水，使具有亲水性的硅铝在分子筛表面排列有序、均匀地沉积在分子筛的表面，并增强了分子筛与硅铝的结合力，避免了无定形硅铝同分子筛之间出现团聚甚至堵塞孔道的现象，而且使硅铝与分子筛的孔道相互贯通，使硅铝和分子筛充分发挥协同作用，有利于活性金属的均匀分布和金属的利用率，提高了催化剂的使用性能。分子筛在引入之前可以根据其使用要求采用各种适宜的方法进行处理，分子筛的改性处理过程不会对复合载体材料产生不利的影响。In the preparation process of the hydrogenation catalyst of the present invention, the molecular sieve is pre-mixed with organic amines, and the organic amines will be pre-adsorbed to the pores and orifices of the molecular sieve, so that the pore structure of the molecular sieve is protected in advance, which can avoid the silica-alumina gelation process Medium fragments enter the pores, block the pores or directly form gels in the pores; at the same time, organic amines have a guiding effect on the silica-alumina pores during the silica-alumina gelation process, and are added during the silica-alumina gelation process. Since the organic matter containing hydroxyl or carboxyl group is soluble in water, the hydrophilic silicon-alumina is arranged in an orderly manner on the surface of the molecular sieve, and evenly deposited on the surface of the molecular sieve, and the binding force between the molecular sieve and the silicon-alumina is enhanced. It avoids the phenomenon of agglomeration or even blockage between amorphous silicon-alumina and molecular sieve, and makes the pores of silicon-aluminum and molecular sieve communicate with each other, so that silicon-alumina and molecular sieve can fully play a synergistic effect, which is conducive to the uniform distribution of active metals and the utilization of metals rate, improving the performance of the catalyst. Molecular sieves can be treated with various appropriate methods according to their use requirements before being introduced, and the modification process of molecular sieves will not have adverse effects on composite carrier materials.
具体实施方式Detailed ways
以浸渍法为例说明本发明加氢催化剂的制备过程，具体如下：催化剂载体材料与粘合剂等其它组分和助剂经混合、碾压、挤条等手段成型，然后进行干燥、焙烧，得到催化剂载体，然后采用常规浸渍方法用含活性金属化合物（比如钼和／或钨、镍和／或钴化合物）溶液浸渍金属，再进行干燥、焙烧得到催化剂产品。其中，催化剂载体材料成型后，干燥条件一般为在80~200℃，干燥1~15小时，焙烧温度一般为450~700℃，焙烧时间一般为1~10小时。催化剂载体浸渍负载活性金属后，催化剂的干燥条件如下：一般为在80~200℃，干燥1~15小时，催化剂的焙烧条件为在350~550℃下焙烧1~8小时。Taking the impregnation method as an example to illustrate the preparation process of the hydrogenation catalyst of the present invention, the details are as follows: the catalyst carrier material and binder and other components and auxiliary agents are formed by mixing, rolling, extruding and other means, and then dried and roasted. The catalyst carrier is obtained, and then the metal is impregnated with a solution containing active metal compounds (such as molybdenum and/or tungsten, nickel and/or cobalt compounds) by a conventional impregnation method, and then dried and calcined to obtain a catalyst product. Among them, after the catalyst carrier material is formed, the drying condition is generally 80-200°C for 1-15 hours, the calcination temperature is generally 450-700°C, and the calcination time is generally 1-10 hours. After the catalyst carrier is impregnated with active metals, the drying conditions of the catalyst are as follows: generally at 80-200°C for 1-15 hours, and the calcination conditions of the catalyst are at 350-550°C for 1-8 hours.
本发明方法中，所述含钼和／或钨、镍和／或钴化合物，可以是由选自含镍和／或钴金属的可溶性化合物中的一种或几种，如它们的硝酸盐、醋酸盐、可溶性碳酸盐、氯化物、可溶性络合物中的一种或几种制备的溶液；可以是由选自含钼和／或钨金属的可溶性化合物中的一种或几种，如钼酸盐、钨酸盐、乙基偏钨酸盐中的一种或几种制备的溶液，可以是由含镍和／或钴金属的可溶性化合物和钼和／或钨金属的可溶性化台物制备的混合溶液；还可以是由含镍和／或钴金属和钼和／或钨金属的杂多酸或盐制备的水溶液。按照本发明提供的方法，对溶液中的溶剂没有限制，可以是有机溶剂，如醇、醚和酸，可以是无机溶剂，如水以及它们的混合物，优选水。In the method of the present invention, said compound containing molybdenum and/or tungsten, nickel and/or cobalt can be selected from one or more of the soluble compounds containing nickel and/or cobalt metal, such as their nitrates, A solution prepared from one or more of acetate, soluble carbonate, chloride, and soluble complex; it can be selected from one or more of soluble compounds containing molybdenum and/or tungsten metal, For example, the solution prepared by one or more of molybdate, tungstate, and ethyl metatungstate can be a soluble compound containing nickel and/or cobalt metal and a soluble compound of molybdenum and/or tungsten metal. It can also be an aqueous solution prepared by heteropolyacid or salt containing nickel and/or cobalt metal and molybdenum and/or tungsten metal. According to the method provided by the present invention, there is no limitation to the solvent in the solution, which may be an organic solvent, such as alcohol, ether and acid, or an inorganic solvent, such as water and mixtures thereof, preferably water.
对于加氢裂化催化剂，加氢活性组分为钼和／或钨及镍和／或钴，以催化剂的重量为基准，以氧化物计，钼和／或钨的含量为5％~40％，优选为12％~35％，镍和／或钴的含量为l％~15％，优选为5％~13％。For the hydrocracking catalyst, the hydrogenation active components are molybdenum and/or tungsten and nickel and/or cobalt, based on the weight of the catalyst, the content of molybdenum and/or tungsten is 5%~40% in terms of oxides, Preferably it is 12%~35%, and the content of nickel and/or cobalt is 1%~15%, preferably 5%~13%.
本发明催化剂制备过程简单、方便，易于操作，适合工业生产。选择适宜的分子筛（改性Y分子筛及改性β分子筛）时，催化剂用于加氢裂化过程，可以有效的提高反应物料在催化剂的传质，提高催化剂的活性及目的产品的选择性，可以获得良好的使用效果。本发明催化剂特别适于处理重质烃物料，重质烃物料的馏程范围在250~600℃，一般在300~550℃，具有上述特点的原料油如瓦斯油、减压馏分油、脱沥清油、催化裂化循环油、页岩油、煤焦油等。反应条件一般在氢气存在条件下，反应压力5~30MPa，氢油体积比100~5000，液时体积空速0.1~5.0h-1，反应温度340~420℃。本发明催化剂在处理通常的VGO时，反应条件一般在氢气存在条件下，反应压力最好10~20MPa，氢油体积比500~2000，液时体积空速0.5~1.5h-1，反应温度370~410℃。The preparation process of the catalyst of the invention is simple, convenient, easy to operate and suitable for industrial production. When choosing a suitable molecular sieve (modified Y molecular sieve and modified β molecular sieve), the catalyst is used in the hydrocracking process, which can effectively improve the mass transfer of the reaction material on the catalyst, improve the activity of the catalyst and the selectivity of the target product, and can obtain Good use effect. The catalyst of the present invention is especially suitable for processing heavy hydrocarbon materials. The distillation range of heavy hydrocarbon materials is 250-600°C, generally 300-550°C. Raw oils with the above characteristics such as gas oil, vacuum distillate oil, Clear oil, catalytic cracking cycle oil, shale oil, coal tar, etc. The reaction conditions are generally in the presence of hydrogen, the reaction pressure is 5~30MPa, the volume ratio of hydrogen to oil is 100~5000, the liquid hourly volume space velocity is 0.1~5.0h-1 , and the reaction temperature is 340~420℃. When the catalyst of the present invention is used to process ordinary VGO, the reaction conditions are generally in the presence of hydrogen, the best reaction pressure is 10~20MPa, the hydrogen-oil volume ratio is 500~2000, the liquid hourly volume space velocity is 0.5~1.5h-1 , and the reaction temperature is 370 ~410°C.
本发明产品的比表面积和孔容是采用低温液氮物理吸附法测定，相对结晶度和晶胞参数采用X射线衍射法测定。钠含量采用等离子发射光谱法测定。本发明中，wt%为质量分数。The specific surface area and pore volume of the product of the invention are measured by a low-temperature liquid nitrogen physical adsorption method, and the relative crystallinity and unit cell parameters are measured by an X-ray diffraction method. Sodium content was determined by plasma emission spectrometry. In the present invention, wt% is mass fraction.
下面结合具体的实施例来进一步说明本发明的制备方法，但是本发明的范围不只限于这些实施例的范围。The preparation method of the present invention will be further described below in conjunction with specific examples, but the scope of the present invention is not limited to the scope of these examples.
实施例Example11
将486g固体氯化铝加入到1升蒸馏水中，同时加热并搅拌至溶解,得到氯化铝溶液(a)。将浓氨水加入适量蒸馏水稀释成约10%稀氨水(b)，93g木糖醇溶解在500ml水中，形成溶液(c)。取10L水玻璃(工业级，模数为3.0)稀释在20L去离子水中，配置成溶液(d)。15g乙醇胺溶于100ml水中，加热至60℃，搅拌状态下加入38g改性Y型分子筛Y-1(SiO2/Al2O3＝11.0, 晶胞常数为24.42Å，相对结晶度为95％)打浆2小时，得到浆液(e)。取一不锈钢反应罐，罐中加入(a)并搅拌加热至65℃后，打开存有(b)的容器的阀门，控制10分钟之内将罐中体系滴加到pH=4.5，继续滴加(b)，打开存有(c)和(e)的容器的阀门，控制30分钟内将罐内体系滴加到pH=8.0，控制(c)和(e)的容器的阀门，保证此时滴加完成。保持温度为65℃，pH=8.0，停留20分钟后，向体系中加入溶液(d)，按照无定形硅铝中二氧化硅的含量为45wt%计算在10分钟内加完。老化1小时，将罐内物料进行过滤，洗涤至无氯离子，过滤，将滤饼在110℃下干燥10小时，粉碎过筛得到催化剂载体干胶粉J-1，经550℃焙烧10小时后，所得的主要物理化学性质见表1。Add 486g of solid aluminum chloride into 1 liter of distilled water while heating and stirring until dissolved to obtain aluminum chloride solution (a). Dilute the concentrated ammonia water into about 10% dilute ammonia water (b) by adding an appropriate amount of distilled water, and dissolve 93g of xylitol in 500ml of water to form a solution (c). Take 10L of water glass (industrial grade, modulus 3.0) and dilute it in 20L of deionized water to prepare solution (d). Dissolve 15g of ethanolamine in 100ml of water, heat to 60°C, add 38g of modified Y-type molecular sieve Y-1 (SiO2 /Al2 O3 =11.0, unit cell constant 24.42Å, relative crystallinity 95%) under stirring Beat for 2 hours to obtain slurry (e). Take a stainless steel reaction tank, add (a) into the tank, stir and heat to 65°C, open the valve of the container containing (b), control the system in the tank to drop to pH = 4.5 within 10 minutes, and continue to drop (b), open the valve of the container containing (c) and (e), control the dropwise addition of the tank system to pH=8.0 within 30 minutes, control the valve of the container of (c) and (e), ensure that at this time Addition is complete. Keep the temperature at 65°C, pH = 8.0, and after staying for 20 minutes, add solution (d) to the system, and complete the addition within 10 minutes based on the silicon dioxide content in amorphous silica-alumina being 45wt%. Aging for 1 hour, filter the material in the tank, wash until there is no chloride ion, filter, dry the filter cake at 110°C for 10 hours, crush and sieve to obtain catalyst carrier dry rubber powder J-1, after roasting at 550°C for 10 hours , and the main physicochemical properties obtained are listed in Table 1.
取产品J-1载体干胶粉80克，粘合剂20克混合，经碾压后挤条成型，干燥并焙烧后置于反应容器中，称取偏钨酸铵50克和硝酸镍23克加水溶解成200毫升溶液，将溶液加入到反应容器浸渍3小时，然后在120℃下干燥，干燥180分钟后，将干燥后的催化剂在500℃焙烧4小时，得到催化剂A，其组成见表2。Take 80 grams of product J-1 carrier dry rubber powder, mix with 20 grams of binder, extrude into strips after rolling, dry and roast and place in a reaction container, weigh 50 grams of ammonium metatungstate and 23 grams of nickel nitrate Add water to dissolve into a 200 ml solution, add the solution to the reaction vessel and soak for 3 hours, then dry at 120°C for 180 minutes, then roast the dried catalyst at 500°C for 4 hours to obtain Catalyst A, the composition of which is shown in Table 2 .
实施例Example22
将120g固体硫酸铝加入到1升蒸馏水中，同时加热并搅拌至溶解,得到硫酸铝溶液(a)。将浓氨水加入适量蒸馏水稀释成约10%稀氨水(b)，18g 1,4-丁二醇溶解在500ml水中，形成溶液(c)。取10L水玻璃(工业级，模数为3.0)稀释在20L去离子水中，配置成溶液(d)。13g乙醇胺溶于100ml水中，加热至60℃，搅拌状态下加入65g改性Y型分子筛Y-1(SiO2/Al2O3＝11.0, 晶胞常数为24.42Å，相对结晶度为95％)打浆2小时，得到浆液(e)。取一不锈钢反应罐，罐中加入(a)并搅拌加热至65℃后，打开存有(b)的容器的阀门，控制10分钟之内将罐中体系滴加到pH=4.5，此时向罐中加入，继续滴加(b) 打开存有(c)和(e)的容器的阀门，控制30分钟内将罐内体系滴加到pH=8.0，控制(c) 和(e)的容器的阀门，保证此时滴加完成。保持温度为65℃，pH=8.0，停留20分钟后，向体系中加入溶液(d)，按照无定形硅铝中二氧化硅的含量为45wt%计算在10分钟内加完。老化1小时，将罐内物料进行过滤，洗涤至无硫酸根离子，过滤，将滤饼在110℃下干燥10小时，粉碎过筛得到催化剂载体干胶粉J-2，经500℃焙烧5小时后，所得的主要物理化学性质见表1。120g of solid aluminum sulfate was added to 1 liter of distilled water while heating and stirring until dissolved to obtain aluminum sulfate solution (a). Add an appropriate amount of distilled water to the concentrated ammonia water and dilute it into about 10% dilute ammonia water (b), and dissolve 18g of 1,4-butanediol in 500ml of water to form a solution (c). Take 10L of water glass (industrial grade, modulus 3.0) and dilute it in 20L of deionized water to prepare solution (d). Dissolve 13g of ethanolamine in 100ml of water, heat to 60°C, add 65g of modified Y-type molecular sieve Y-1 (SiO2 /Al2 O3 =11.0, unit cell constant 24.42Å, relative crystallinity 95%) under stirring Beat for 2 hours to obtain slurry (e). Take a stainless steel reaction tank, add (a) into the tank, stir and heat to 65°C, open the valve of the container containing (b), and control the system in the tank to drop to pH=4.5 within 10 minutes, at this time, add Add in the tank, continue to drop (b) open the valve of the container containing (c) and (e), control the system in the tank to drop to pH=8.0 within 30 minutes, control the container of (c) and (e) The valve ensures that the dripping is completed at this time. Keep the temperature at 65°C, pH = 8.0, and after staying for 20 minutes, add solution (d) to the system, and complete the addition within 10 minutes based on the silicon dioxide content in amorphous silica-alumina being 45wt%. Aging for 1 hour, filter the material in the tank, wash until there is no sulfate ion, filter, dry the filter cake at 110°C for 10 hours, crush and sieve to obtain catalyst carrier dry rubber powder J-2, and roast at 500°C for 5 hours The main physicochemical properties obtained are listed in Table 1.
取产品J-2载体干胶粉80克，粘合剂20克混合，经碾压后挤条成型，干燥并焙烧后置于反应容器中，称取偏钨酸铵50克和硝酸镍23克加水溶解成200毫升溶液，将溶液加入到反应容器浸渍3小时，然后在120℃下干燥，干燥180分钟后，将干燥后的催化剂在500℃焙烧4小时，得到催化剂B，其组成见表2。Take 80 grams of product J-2 carrier dry rubber powder, mix with 20 grams of binder, extrude into strips after rolling, dry and roast and place in a reaction container, weigh 50 grams of ammonium metatungstate and 23 grams of nickel nitrate Add water to dissolve into a 200 ml solution, add the solution to the reaction vessel and soak for 3 hours, then dry at 120°C for 180 minutes, then roast the dried catalyst at 500°C for 4 hours to obtain Catalyst B, the composition of which is shown in Table 2 .
实施例Example33
将120g固体硫酸铝加入到1升蒸馏水中，同时加热并搅拌至溶解,得到硫酸铝溶液(a)。将固体偏铝酸钠配制成浓度为20g Al2O3/l铝酸钠溶液 (b)。36g1,4-丁二酸溶解在1L水中，形成溶液(c)。57g乙二胺溶于500ml水中，加热到60℃，搅拌状态下加入572g改性Y型分子筛Y-1(SiO2/Al2O3＝11.0, 晶胞常数为24.42Å，相对结晶度为95％)，继续搅拌2小时后得到浆液(d)。取10L水玻璃(工业级，模数为3.0)稀释在20L去离子水中，配置成溶液(e)。取一钢制反应罐，置入2l去离子水搅拌加热至65℃后，同时打开存有(a) 、(b)、(c)和(d)的容器的阀门，控制体系的pH=8.0，控制45分钟内将(a) (c)和(d)滴完。保持温度为65℃，pH=8.0，停留20分钟后，向体系中加入溶液(e)，按照无定形硅铝中二氧化硅的含量50wt%计算在10分钟内加完。老化1小时，将罐内物料进行过滤，洗涤至无硫酸根离子，过滤，将滤饼在110℃下干燥10小时，粉碎过筛得到催化剂载体干胶粉J-3，经500℃焙烧5小时后，所得的粉碎过筛得到载体材料J-3。主要物理化学性质见表1。120g of solid aluminum sulfate was added to 1 liter of distilled water while heating and stirring until dissolved to obtain aluminum sulfate solution (a). Prepare the solid sodium metaaluminate to a concentration of 20g Al2 O3 /l sodium aluminate solution (b). 36 g of 1,4-butanedioic acid was dissolved in 1 L of water to form solution (c). Dissolve 57g of ethylenediamine in 500ml of water, heat to 60°C, add 572g of modified Y-type molecular sieve Y-1 (SiO2 /Al2 O3 =11.0, unit cell constant 24.42 Å, relative crystallinity 95 %), after continuing to stir for 2 hours, slurry (d) was obtained. Take 10L water glass (industrial grade, modulus 3.0) and dilute it in 20L deionized water to prepare solution (e). Take a steel reaction tank, put 2l of deionized water into it, stir and heat it to 65°C, open the valves of the containers containing (a), (b), (c) and (d) at the same time, and control the pH of the system to 8.0 , Control (a) (c) and (d) to drop within 45 minutes. Keep the temperature at 65°C, pH = 8.0, and after staying for 20 minutes, add solution (e) to the system, and add it within 10 minutes based on the silicon dioxide content of 50wt% in amorphous silica-alumina. Aging for 1 hour, filter the material in the tank, wash until there is no sulfate ion, filter, dry the filter cake at 110°C for 10 hours, crush and sieve to obtain catalyst carrier dry rubber powder J-3, and roast at 500°C for 5 hours Afterwards, the resulting pulverization was sieved to obtain carrier material J-3. The main physical and chemical properties are listed in Table 1.
取产品J-3载体干胶粉80克，粘合剂20克混合，经碾压后挤条成型，干燥并焙烧后置于反应容器中，称取偏钨酸铵50克和硝酸镍23克加水溶解成200毫升溶液，将溶液加入到反应容器浸渍3小时，然后在120℃下干燥，干燥180分钟后，将干燥后的催化剂在500℃焙烧4小时，得到催化剂C，其组成见表2。Take the product J-3 carrier dry rubber powder 80 grams, mix with 20 grams of binder, extrude into strips after rolling, dry and roast and place in the reaction container, weigh 50 grams of ammonium metatungstate and 23 grams of nickel nitrate Add water to dissolve into a 200 ml solution, add the solution to the reaction vessel and soak for 3 hours, then dry at 120°C for 180 minutes, then roast the dried catalyst at 500°C for 4 hours to obtain Catalyst C, the composition of which is shown in Table 2 .
实施例Example44
将654g固体氯化铝加入到1升蒸馏水中，同时加热并搅拌至溶解,得到氯化铝溶液(a)。将浓氨水加入适量蒸馏水稀释成约10%稀氨水(b)，125g甘露醇溶解在1L水中，形成溶液(c)。取10L水玻璃(工业级，模数为3.0)稀释在20L去离子水中，配置成溶液(d)。9.5g1,4-丁二胺溶于100ml水中，加热到60℃，加入24g改性的氢型β沸石 (SiO2/Al2O3＝30.0, 晶胞常数为12.00Å，相对结晶度为90％)继续搅拌2小时，得到浆液(e)。取一钢制反应罐，罐中加入(a)并搅拌加热至65℃后，打开存有(b)的容器的阀门，控制10分钟之内将罐中体系滴加到pH=4.0，继续滴加(b)，打开存有(c)和(e)的容器的阀门，控制30分钟内将罐内体系滴加到pH=8.0，控制(c)和(e)的容器的阀门，保证此时滴加完成。保持温度为65℃，pH=8.0，停留20分钟后，向体系中加入溶液(d)，按照无定形硅铝中二氧化硅的含量45wt%计算在10分钟内加完。老化1小时，将罐内物料进行过滤，洗涤至无氯离子，过滤，将滤饼在110℃下干燥10小时，粉碎过筛得到催化剂载体干胶粉J-4，经500℃焙烧5小时后，所得的主要物理化学性质见表1。Add 654g of solid aluminum chloride into 1 liter of distilled water while heating and stirring until dissolved to obtain aluminum chloride solution (a). Add an appropriate amount of distilled water to the concentrated ammonia water and dilute it into about 10% dilute ammonia water (b), and dissolve 125g of mannitol in 1L of water to form a solution (c). Take 10L of water glass (industrial grade, modulus 3.0) and dilute it in 20L of deionized water to prepare solution (d). Dissolve 9.5g of 1,4-butanediamine in 100ml of water, heat to 60°C, add 24g of modified hydrogen-type zeolite beta (SiO2 /Al2 O3 =30.0, unit cell constant is 12.00Å, relative crystallinity is 90 %) to continue stirring for 2 hours to obtain slurry (e). Take a steel reaction tank, add (a) into the tank, stir and heat to 65°C, open the valve of the container containing (b), control the system in the tank to drop to pH=4.0 within 10 minutes, and continue to drop Add (b), open the valve of the container containing (c) and (e), control the dropwise addition of the tank system to pH=8.0 within 30 minutes, control the valve of the container of (c) and (e) to ensure this When the dropwise addition is complete. Keep the temperature at 65°C, pH = 8.0, and after staying for 20 minutes, add solution (d) to the system, and complete the addition within 10 minutes based on the silicon dioxide content of 45wt% in the amorphous silica-alumina. Aging for 1 hour, filter the material in the tank, wash until there is no chloride ion, filter, dry the filter cake at 110°C for 10 hours, crush and sieve to obtain catalyst carrier dry rubber powder J-4, after roasting at 500°C for 5 hours , and the main physicochemical properties obtained are listed in Table 1.
取产品J-4载体干胶粉80克，粘合剂20克混合，经碾压后挤条成型，干燥并焙烧后置于反应容器中，称取偏钨酸铵50克和硝酸镍23克加水溶解成200毫升溶液，将溶液加入到反应容器浸渍3小时，然后在120℃下干燥，干燥180分钟后，将干燥后的催化剂在500℃焙烧4小时，得到催化剂D，其组成见表2。Take 80 grams of product J-4 carrier dry rubber powder, mix with 20 grams of binder, extrude into strips after rolling, dry and roast and place in a reaction container, weigh 50 grams of ammonium metatungstate and 23 grams of nickel nitrate Add water to dissolve into a 200 ml solution, add the solution to the reaction vessel and soak for 3 hours, then dry at 120°C for 180 minutes, then roast the dried catalyst at 500°C for 4 hours to obtain Catalyst D, the composition of which is shown in Table 2 .
对比例comparative example11
重复实施例2的合成，不添加乙醇胺及1,4-丁二醇，制得对比载体干胶粉DF-1。经500℃焙烧5小时后，所得的主要物理化学性质见表1。The synthesis of Example 2 was repeated without adding ethanolamine and 1,4-butanediol to prepare the comparative carrier dry rubber powder DF-1. After calcination at 500°C for 5 hours, the main physical and chemical properties obtained are shown in Table 1.
载体材料DF-1合成催化剂的过程同实施例2，得到催化剂DA，其组成见表2。The process of synthesizing the catalyst with the carrier material DF-1 is the same as in Example 2 to obtain the catalyst DA, whose composition is shown in Table 2.
对比例comparative example22
重复实施例2的合成，不添加乙醇胺，制得对比载体干胶粉材料DF-2。经500℃焙烧5小时后，所得的主要物理化学性质见表1。Repeat the synthesis of Example 2 without adding ethanolamine to prepare the comparative carrier dry rubber powder material DF-2. After calcination at 500°C for 5 hours, the main physical and chemical properties obtained are shown in Table 1.
载体材料DF-2合成催化剂的过程同实施例2，得到催化剂DB，其组成见表2。The process of synthesizing the catalyst with the carrier material DF-2 is the same as in Example 2 to obtain the catalyst DB, the composition of which is shown in Table 2.
对比例comparative example33
重复实施例2的合成，不添加Y型分子筛和乙醇胺及1,4-丁二醇，制得对比载体干胶粉DF-3。经500℃焙烧5小时后，所得的主要物理化学性质见表1。The synthesis of Example 2 was repeated without adding Y-type molecular sieves, ethanolamine and 1,4-butanediol to prepare the comparative carrier dry rubber powder DF-3. After calcination at 500°C for 5 hours, the main physical and chemical properties obtained are shown in Table 1.
载体材料DF-2合成催化剂的过程同实施例2，得到催化剂DC，其组成见表2。The process of synthesizing the catalyst with carrier material DF-2 is the same as in Example 2 to obtain the catalyst DC, whose composition is shown in Table 2.
对比例comparative example44
重复实施例4的合成，不添加有机胺及有机醇，制得对比载体干胶粉DF-4。经500℃焙烧5小时后，所得的主要物理化学性质见表1。The synthesis of Example 4 was repeated without adding organic amines and organic alcohols to prepare the comparative carrier dry rubber powder DF-4. After calcination at 500°C for 5 hours, the main physical and chemical properties obtained are shown in Table 1.
载体材料DF-4合成催化剂的过程同实施例4，得到催化剂DD，其组成见表2。The process of synthesizing the catalyst with the carrier material DF-4 is the same as in Example 4 to obtain the catalyst DD, whose composition is shown in Table 2.
对比例comparative example55
重复实施例4的合成，不添加氢型β分子筛和有机胺及有机醇，制得对比载体干胶粉DF-5。经500℃焙烧5小时后，所得的主要物理化学性质见表1。The synthesis of Example 4 was repeated without adding hydrogen-type β molecular sieves, organic amines and organic alcohols to prepare the comparative carrier dry rubber powder DF-5. After calcination at 500°C for 5 hours, the main physical and chemical properties obtained are shown in Table 1.
载体材料DF-4合成催化剂的过程同实施例4，得到催化剂DE，其组成见表2。The process of synthesizing the catalyst with carrier material DF-4 is the same as in Example 4 to obtain the catalyst DE, whose composition is shown in Table 2.
表1 载体干胶粉主要性质Table 1 Main properties of carrier dry rubber powder
表1续 载体干胶粉主要性质Table 1 continuedMain properties of carrier dry rubber powder
通过表1数据对比看以看出，使用本方法所制得的分子筛-无定形硅铝复合载体干胶粉比表面积和孔容得到了大大的提高，可以有效的解决在成胶时造成的无定形硅铝同分子筛之间的团聚甚至堵塞的问题；使用本方法所制得的载体干胶粉在物化性质上跟无定形硅铝和分子筛的物理混合物的数据接近，更加说明了使用本方法在保留分子筛和无定形硅铝的个体性质上的优越性。通过本方法可以制备出一种无定形硅铝和分子筛有机复合的、高度分散的大孔容大比表面的催化剂载体干胶粉。By comparing the data in Table 1, it can be seen that the specific surface area and pore volume of the molecular sieve-amorphous silicon-aluminum composite carrier dry rubber powder prepared by this method have been greatly improved, and can effectively solve the problem of unnecessary gelation. The problem of agglomeration or even blockage between amorphous silica-alumina and molecular sieve; the physical and chemical properties of the carrier dry rubber powder prepared by this method are close to the data of the physical mixture of amorphous silica-alumina and molecular sieve, which further illustrates the use of this method in The advantages of individual properties of molecular sieve and amorphous silica alumina are retained. The method can prepare a highly dispersed catalyst carrier dry rubber powder with large pore volume and large specific surface, which is organically compounded by amorphous silicon-alumina and molecular sieve.
表2 催化剂的组成和性质Table 2 Composition and properties of catalysts
将上述本发明催化剂及其对比催化剂进行评价。评价用原料油为伊朗VGO，性质见表3，评价条件如下：反应压力14MPa，氢油体积比1500，液时体积空速1.5 h-1。主要性质见表4。The catalysts of the invention described above and their comparative catalysts were evaluated. The raw material oil used for evaluation is Iranian VGO. The properties are shown in Table 3. The evaluation conditions are as follows: reaction pressure 14MPa, hydrogen-oil volume ratio 1500, liquid hourly volume space velocity 1.5 h-1 . The main properties are shown in Table 4.
表3原料油的性质 Table 3 Properties of raw oil
表4 评价结果 Table 4 Evaluation Results
从评价结果可以看出，使用本发明方法制备的催化剂具有较好的活性及产品选择性。It can be seen from the evaluation results that the catalyst prepared by the method of the present invention has better activity and product selectivity.
| Application Number | Priority Date | Filing Date | Title |
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| CN201110355819.6ACN103100406B (en) | 2011-11-11 | 2011-11-11 | Method for preparing hydrogenation catalyst |
| Application Number | Priority Date | Filing Date | Title |
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| CN201110355819.6ACN103100406B (en) | 2011-11-11 | 2011-11-11 | Method for preparing hydrogenation catalyst |
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| CN103100406A CN103100406A (en) | 2013-05-15 |
| CN103100406Btrue CN103100406B (en) | 2014-09-17 |
| Application Number | Title | Priority Date | Filing Date |
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| CN201110355819.6AActiveCN103100406B (en) | 2011-11-11 | 2011-11-11 | Method for preparing hydrogenation catalyst |
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