阅读说明：本技术 一种燃料油加氢精制催化剂的制法 (Preparation method of fuel oil hydrofining catalyst ) 是由 沈俭一 袁亚梅 陈慧 傅玉川 于 2018-08-14 设计创作，主要内容包括：本发明公开了一种含高分散Ni-P-S活性物种的燃料油加氢精制催化剂的制备方法,属多相催化技术领域。制备的加氢精制催化剂以Ni<Sub>2</Sub>P为主要物相,含有一定量的硫。磷与镍的摩尔比为0.3～2,硫含量为0.5～5wt％。由于采用了高分散的Ni<Sub>2</Sub>P为前体,所获得的含Ni-P-S活性物种的加氢精制催化剂具有很高的活性。(The invention discloses a preparation method of a fuel oil hydrofining catalyst containing high-dispersion Ni-P-S active species, belonging to the technical field of heterogeneous catalysis. The prepared hydrofining catalyst is made of Ni 2 P is the main phase and contains a certain amount of sulfur. The molar ratio of phosphorus to nickel is 0.3-2, and the sulfur content is 0.5-5 wt%. Due to the use of highly dispersed Ni 2 P is a precursor, and the obtained hydrofining catalyst containing Ni-P-S active species has high activity.)

1. A preparation method of a nickel phosphide catalyst containing high-dispersion Ni-P-S active species for fuel oil hydrofining reaction is characterized by comprising the following steps: and (2) vulcanizing the high-dispersion nickel phosphide catalyst serving as a precursor, wherein the sulfur content of the vulcanized nickel phosphide catalyst is 0.5-5 wt%.

2. The highly dispersed nickel phosphide catalyst according to claim 1, wherein the molar ratio of phosphorus to nickel is 0.3 to 2.

3. The highly dispersed nickel phosphide catalyst of claim 1, prepared by a process for the phosphating of a highly dispersed nickel catalyst precursor.

4. The process of claim 1, wherein the sulfidation of the highly dispersed nickel phosphide catalyst is carried out by passing an organic solution containing a metered amount of organic sulfur through a bed of nickel phosphide catalyst in a flowing atmosphere.

Technical Field

The invention relates to a preparation method of a hydrofining catalyst, belonging to the technical field of heterogeneous catalysis.

Technical Field

Transition metal sulfide is traditionally used as a catalyst in the hydrofining process of fuel oil, but with the increasing strictness of environmental protection requirements, the traditional catalyst is more and more difficult to meet the regulatory requirements, and a novel efficient hydrofining catalyst must be developed. Non-sulfide catalysts such as transition metal carbides, nitrides and phosphides have been of interest to researchers for over two decades, especially nickel phosphide (Ni)₂P) catalysts have higher Hydrodesulfurization (HDS) activity and stability than conventional metal sulfides, and are considered as a new generation of hydrofinishing catalysts expected to replace conventional sulfide catalysts.

It has been found that nickel phosphide reacts with H formed in the hydrodesulfurization reaction₂S acts to form Ni-P-S species on the catalyst surface, which are likely to be the active phase of the HDS reaction (Oyama et al, J.Catal., 2004, Vol.221, pp.263-273). Therefore, some researchers have tried to prepare Ni₂Ni-P-S active species are introduced on the surface of the P catalyst to improve the HDS activity of the catalyst. For example, CN1850335A discloses a metal sulfide-phosphide hydrofining catalyst, which uses a supported metal oxide and a supported phosphate to prepare a phosphide precursor, and then the precursor is added in H₂S/H₂Presulfiding in an atmosphere and then in H₂Reducing in atmosphere to obtain the metal sulfide phosphide catalyst. CN102994142A discloses a method for hydrorefining pyrolysis gasoline, the active components of the catalyst are one or more metal sulfides of Co, Mo, Ni and W and Ni₂P is a composite catalyst. The preparation process of the catalyst is essentially that Ni is synthesized firstly₂Catalyst precursor of P phase, and H₂S is pre-vulcanized to obtain the product. CN104174418A discloses a method for synthesizing nickel phosphide catalyst based on nickel sulfide, which uses mechanical mixture of nickel sulfide and sodium hypophosphite as precursor, and utilizes the reaction of nickel ions and phosphine to form nickel phosphide, and the hydrogen sulfide generated at the same time can construct Ni-P-S active species on the surface of nickel phosphide. CN104941673A also discloses a sulfur-containing nickel phosphide catalyst, which is prepared by sulfidation of nickel phosphide or low-temperature reduction of phosphorus sulfide, and preferably the latter. However, it has been reported that Ni is used in the preparation of the above-mentioned sulfur-containing nickel phosphide catalyst₂The P catalyst is prepared by a Temperature Programmed Reduction (TPR) method, and relates to high-temperature reaction, the finally obtained catalyst has low dispersity, and the number of active centers in unit surface area is low, so that the hydrofining activity is not ideal. The same is true for the first preparation of nickel phosphorus sulfide and the subsequent reduction with hydrogen. The reason for this is that the dispersion of Ni-P-S active species obtained by any method depends on the precursor Ni₂Dispersity of P or NiS. Ni obtained by the production method used in the above-mentioned document₂The grain size of P or NiS is larger due to the limitation of the preparation method, so that the dispersity of Ni-P-S active species is lower, and the hydrofining activity is not high.

Based on the above analysis, if Ni-P-S active species with high dispersion are to be prepared, highly dispersed Ni must be prepared first₂P or NiS precursors. The present invention providesA method for preparing a high-dispersion Ni-P-S composite hydrofining catalyst comprises the following steps: preparing high-dispersion supported nickel catalyst as precursor, and converting it into high-dispersion Ni₂P or NiS precursor, and further converted into Ni-P-S composite catalyst. The Ni-P-S active species obtained by the method have high dispersity, small particle size (6-12 nm), and high HDS activity and stability.

Disclosure of Invention

The technical scheme of the invention is as follows:

a preparation method of a nickel phosphide catalyst containing high-dispersion Ni-P-S active species for fuel oil hydrofining reaction is characterized by comprising the following steps: and (2) vulcanizing the high-dispersion nickel phosphide catalyst serving as a precursor, wherein the sulfur content of the vulcanized nickel phosphide catalyst is 0.5-5 wt%.

The molar ratio of phosphorus to nickel in the high-dispersion nickel phosphide catalyst is 0.3-2.

The high-dispersion nickel phosphide catalyst is prepared by a method of phosphating a high-dispersion nickel catalyst precursor, and the high-dispersion nickel catalyst is preferably prepared by a coprecipitation method.

The sulfuration method of the high-dispersion nickel phosphide catalyst is realized by passing an organic solution containing a certain amount of organic sulfur through a nickel phosphide catalyst bed layer in a flowing atmosphere at a certain temperature. The process can be carried out by the method disclosed in the technical field, such as the method described in CN 104772154A.

By adopting the technical scheme, the process is simple, the operation is simple and convenient, and the Ni-P-S active species in the obtained nickel phosphide catalyst containing the high-dispersion Ni-P-S active species has high dispersion degree and higher hydrodesulfurization reaction activity of dibenzothiophene.

Detailed Description

The invention is further illustrated by the following examples: