本文選題：水熱法 + 石油精煉��； 參考：《中國海洋大學》2010年碩士論文

【摘要】：隨著環(huán)境的惡化和石油重質化和劣質化的趨勢越來越嚴重,對高性能石油加氫精制催化劑的要求越來越迫切。Ni-P化合物是近年來發(fā)展起來的一種新型的石油精煉催化劑,具有廣泛的應用前景。因此,研究制備具有高催化性能的Ni-P化合物成為當今石油精煉催化材料研究的熱點。 本文采用水熱法制備新型石油精煉催化材料Ni-P化合物,研究了制備過程中各工藝條件對產(chǎn)物的影響。利用XRD、SEM、TEM、EDS等手段對產(chǎn)物物相及形貌進行了表征分析。主要研究結果如下： (一)水熱法制備Ni2P和Ni12P5微米級粉體及其表征 以紅磷和氯化鎳為原料,通過水熱法制備Ni2P和Ni12P5微米級粉體,在此基礎上系統(tǒng)的研究P/Ni比、水熱溫度、水熱時間對產(chǎn)物物相和形貌的影響。結果表明： 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；改變P/Ni比對產(chǎn)物的形貌沒有太大的影響,產(chǎn)物基本保持了紅磷的原始形貌；紅磷與Ni2+反應生成Ni2P、Ni12P5的反應是固-液反應機理,溶液中的Ni2+滲透入紅磷表面與其反應,從而使產(chǎn)物保持了紅磷的原始形貌。 2)200℃以下產(chǎn)物為Ni2P物相,在此溫度范圍內改變水熱溫度對產(chǎn)物的物相沒有影響,水熱溫度提高到210℃時有利于Ni12P5的生成,不利于Ni2P的生成。 3)水熱時間從12h延長到24h,產(chǎn)物物相都是純凈的Ni2P相,但是當將水熱時間從24h延長到48h時,生成了純凈的Ni12P5。延長水熱時間更有利于Ni12P5物相的生成；延長水熱時間對產(chǎn)物的形貌沒有影響。 (二)水熱法制備Ni2P和Ni12P5納米級粉體及其表征 水熱法制備Ni2P和Ni12P5納米級粉體,通過改變原料的P/Ni比、水熱溫度、水熱時間制備出較為純凈的Ni2P和Ni12P5納米粉體。在此基礎上系統(tǒng)的研究P/Ni比、水熱溫度、水熱時間對產(chǎn)物物相和形貌的影響。結果表明： 1)在低P/Ni比(P/Ni≤15/1)時,產(chǎn)物中以Ni12P5為主,而在高P/Ni比(P/Ni≥18/1)時,產(chǎn)物以Ni2P為主。所以,增大P/Ni比更有利于Ni2P的生成,而不利于Ni12P5的生成。從改變P/Ni比所得產(chǎn)物及水熱處理過的紅磷的透射電鏡照片可以看出,產(chǎn)物繼承了水熱處理過紅磷的不規(guī)則形貌,改變反應的P/Ni比不會對產(chǎn)物的形貌造成明顯的影響。 2)在首先將紅磷在200℃,水熱處理24h后,P：Ni=30：1、水熱時間24h為不變條件下,200℃是生成Ni2P的理想條件,溫度升高或降低都會導致產(chǎn)物中次要相Ni12P5的出現(xiàn)。水熱溫度從190℃升到200℃再升到210℃并沒有改變產(chǎn)物的類似紅磷的不規(guī)則形貌。 3)改變水熱時間對物相的影響是巨大的,在不同的時間段上有不同的產(chǎn)物生成。 (三)球形Ni-P化合物的制備及表征 采用NaH2PO3·H2O做磷源,與NiCl2·6H2O在不同的水熱條件下反應,成功制備了具有球形形貌的鎳-磷化合物,XRD測試結果證明產(chǎn)物結晶良好,通過EDS測試得知產(chǎn)物的元素組成為磷和鎳兩種元素,是一種富鎳的Ni-P化合物。提高原料中P/Ni值,產(chǎn)物中的P/Ni值也會提高,延長水熱時間也會提高產(chǎn)物中的P/Ni值。原料中的P/Ni值及水熱時間的改變對產(chǎn)物的形貌、化學組成均無顯著的影響。
[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.
【學位授予單位】：中國海洋大學
【學位級別】：碩士
【學位授予年份】：2010
【分類號】：TE624.9

【引證文獻】

相關碩士學位論文 前1條

1 王波;鎳、鈷、錫磷化物的水熱合成與表征[D];中國海洋大學;2012年

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本文編號：1995951