新型石油精炼催化剂Ni-P化合物的水热法制备研究

发布时间：2018-06-08 13:29

  本文选题：水热法 + 石油精炼　； 参考：《中国海洋大学》2010年硕士论文

【摘要】：随着环境的恶化和石油重质化和劣质化的趋势越来越严重,对高性能石油加氢精制催化剂的要求越来越迫切。Ni-P化合物是近年来发展起来的一种新型的石油精炼催化剂,具有广泛的应用前景。因此,研究制备具有高催化性能的Ni-P化合物成为当今石油精炼催化材料研究的热点。 本文采用水热法制备新型石油精炼催化材料Ni-P化合物,研究了制备过程中各工艺条件对产物的影响。利用XRD、SEM、TEM、EDS等手段对产物物相及形貌进行了表征分析。主要研究结果如下： (一)水热法制备Ni2P和Ni12P5微米级粉体及其表征 以红磷和氯化镍为原料,通过水热法制备Ni2P和Ni12P5微米级粉体,在此基础上系统的研究P/Ni比、水热温度、水热时间对产物物相和形貌的影响。结果表明： 1)提高P/Ni比有助于Ni2P的生成,降低P/Ni比有助于Ni12P5的生成；改变P/Ni比对产物的形貌没有太大的影响,产物基本保持了红磷的原始形貌；红磷与Ni2+反应生成Ni2P、Ni12P5的反应是固-液反应机理,溶液中的Ni2+渗透入红磷表面与其反应,从而使产物保持了红磷的原始形貌。 2)200℃以下产物为Ni2P物相,在此温度范围内改变水热温度对产物的物相没有影响,水热温度提高到210℃时有利于Ni12P5的生成,不利于Ni2P的生成。 3)水热时间从12h延长到24h,产物物相都是纯净的Ni2P相,但是当将水热时间从24h延长到48h时,生成了纯净的Ni12P5。延长水热时间更有利于Ni12P5物相的生成；延长水热时间对产物的形貌没有影响。 (二)水热法制备Ni2P和Ni12P5纳米级粉体及其表征 水热法制备Ni2P和Ni12P5纳米级粉体,通过改变原料的P/Ni比、水热温度、水热时间制备出较为纯净的Ni2P和Ni12P5纳米粉体。在此基础上系统的研究P/Ni比、水热温度、水热时间对产物物相和形貌的影响。结果表明： 1)在低P/Ni比(P/Ni≤15/1)时,产物中以Ni12P5为主,而在高P/Ni比(P/Ni≥18/1)时,产物以Ni2P为主。所以,增大P/Ni比更有利于Ni2P的生成,而不利于Ni12P5的生成。从改变P/Ni比所得产物及水热处理过的红磷的透射电镜照片可以看出,产物继承了水热处理过红磷的不规则形貌,改变反应的P/Ni比不会对产物的形貌造成明显的影响。 2)在首先将红磷在200℃,水热处理24h后,P：Ni=30：1、水热时间24h为不变条件下,200℃是生成Ni2P的理想条件,温度升高或降低都会导致产物中次要相Ni12P5的出现。水热温度从190℃升到200℃再升到210℃并没有改变产物的类似红磷的不规则形貌。 3)改变水热时间对物相的影响是巨大的,在不同的时间段上有不同的产物生成。 (三)球形Ni-P化合物的制备及表征 采用NaH2PO3·H2O做磷源,与NiCl2·6H2O在不同的水热条件下反应,成功制备了具有球形形貌的镍-磷化合物,XRD测试结果证明产物结晶良好,通过EDS测试得知产物的元素组成为磷和镍两种元素,是一种富镍的Ni-P化合物。提高原料中P/Ni值,产物中的P/Ni值也会提高,延长水热时间也会提高产物中的P/Ni值。原料中的P/Ni值及水热时间的改变对产物的形貌、化学组成均无显著的影响。
[Abstract]:With the deterioration of the environment and the increasing tendency of heavy oil and inferior quality, the requirements for the high performance petroleum hydrofining catalyst are becoming more and more urgent, and.Ni-P is a new kind of petroleum refining catalyst developed in recent years, which has a wide application prospect. Therefore, the preparation of Ni-P synthesis with high catalytic performance has been studied. Materials have become a hot topic in petroleum refining catalytic materials.
In this paper, a new type of petroleum refining catalytic material Ni-P was prepared by hydrothermal method. The effects of various process conditions on the product were studied. The phase and morphology of the products were characterized by means of XRD, SEM, TEM and EDS. The main results were as follows:
(1) hydrothermal synthesis of Ni2P and Ni12P5 micron sized powders and their characterization
With red phosphorus and nickel chloride as raw materials, Ni2P and Ni12P5 micron grade powders were prepared by hydrothermal method. On this basis, the effects of P/Ni ratio, hydrothermal temperature and hydrothermal time on the phase and morphology of the products were systematically studied.
1) increasing the P/Ni ratio is helpful to the generation of Ni2P, and the reduction of P/Ni ratio is helpful to the formation of Ni12P5; the change of P/Ni has not much influence on the morphology of the product. The product basically maintains the original morphology of the red phosphorus; the reaction of red phosphorus and Ni2+ generates Ni2P, the reaction of Ni12P5 is a solid liquid reaction mechanism, and the Ni2+ permeation into the surface of the red phosphorus in the solution is from the reaction, from the reaction, and from the reaction, from the reaction, from the reaction of the Ni12P5 in the solution, and from the reaction of the reaction of the solution to the surface of the red phosphorus. The product kept the original morphology of red phosphorus.
2) the product under 200 centigrade is Ni2P phase. The change of water heat temperature in this temperature range has no effect on the phase of the product. When the temperature of water is raised to 210, it is beneficial to the formation of Ni12P5, which is not conducive to the formation of Ni2P.
3) the hydrothermal time extended from 12h to 24h, the product phase was pure Ni2P phase, but when the hydrothermal time was extended from 24h to 48h, the pure Ni12P5. extended hydrothermal time was more beneficial to the formation of Ni12P5 phase, and the prolongation of the hydrothermal time had no effect on the morphology of the products.
(two) hydrothermal synthesis of Ni2P and Ni12P5 nanoscale powders and their characterization
Ni2P and Ni12P5 nanoscale powders were prepared by hydrothermal method. The pure Ni2P and Ni12P5 nano powders were prepared by changing the P/Ni ratio of the raw materials, the hydrothermal temperature and the hydrothermal time. On this basis, the effects of P/Ni ratio, hydrothermal temperature and hydrothermal time on the phase and morphology of the products were systematically studied.
1) at a low P/Ni ratio (P/Ni < 15/1), the product is dominated by Ni12P5, while Ni2P is the dominant product at a high P/Ni ratio (P/Ni > 18/1). Therefore, the increase of the P/Ni ratio is more conducive to the formation of Ni2P, but is not conducive to the production of Ni12P5. The irregular morphology of red phosphorus can change the P/Ni ratio of the reaction obviously.
2) when the red phosphorus is at 200, the water heat treatment 24h, P:Ni=30:1 and the hydrothermal time 24h are the same conditions, 200 is the ideal condition for the formation of Ni2P. The temperature rise or decrease will lead to the emergence of secondary phase Ni12P5 in the product. The hydrothermal temperature rises from 190 C to 200 c and then rises to 210 centigrade, and does not change the irregular shape of the product similar to red phosphorus Appearance.
3) the effect of changing hydrothermal time on the phase is enormous, and different products are generated at different time intervals.
(three) preparation and characterization of spherical Ni-P compounds
NaH2PO3 H2O was used as phosphorus source and NiCl2 / 6H2O was reacted under different hydrothermal conditions. The nickel phosphorus compound with spherical morphology was successfully prepared. The result of XRD test showed that the product crystallized well. Through EDS test, the composition of the product was composed of two elements of phosphorus and nickel. It was a kind of nickel rich Ni-P compound. It improved the P/Ni value in the raw material and the product. The P/Ni value also increased, and the P/Ni value in the product was increased by prolonging the hydrothermal time. The changes in the P/Ni value and the hydrothermal time in the raw material had no significant effect on the morphology and chemical composition of the products.
【学位授予单位】：中国海洋大学
【学位级别】：硕士
【学位授予年份】：2010
【分类号】：TE624.9

【引证文献】

相关硕士学位论文 前1条

1 王波;镍、钴、锡磷化物的水热合成与表征[D];中国海洋大学;2012年

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