Ultra-deep desulfurization absorbent containing C 4 conjugated dienes raw material and production method and use thereof

Abstract

The invention relates to an adsorbent for deep desulfurization of materials containing C5 conjugated alkadiene, a preparation method and application thereof. The adsorbent for desulfurization consists of reduced VIII transition metal, reduced IB transition metal which activate sulfur-containing molecules, and alumina carrier. The adsorbent can adsorb nearly all sulfur compounds in the materials containing C5 conjugated alkadiene to get the materials containing C5 conjugated alkadiene with sulfur content lower than 10ng / mu l.

Description

technical field [0001] The invention relates to a carbon five-conjugated diene raw material ultra-deep desulfurization adsorbent, its preparation method and application. Background technique [0002] The C5-containing conjugated diene raw material is used as a by-product of the ethylene plant and is mainly used to produce high value-added products - hydrogenated petroleum resins. Conjugated dienes such as isoprene, cyclopentadiene and piperylene are the main components used in the production of petroleum resins in C5-containing conjugated diene raw materials, which are highly chemically active. The content of isoprene, cyclopentadiene and piperylene accounts for about 45% to 55% of the cracked C5 fraction. Among them, cyclopentadiene accounts for 15%-15%, isoprene accounts for 15%-20%, and piperylene accounts for 10%-20%. At the same time, the carbon five raw materials also contain trace (10-200ppm) sulfur-containing impurities, usually carbonyl sulfide, mercaptan, sulfide...

AI Technical Summary

Problems solved by technology

The traditional method is to use the combination of alcohol amine desulfurization, alkali elution desulfurization and Merox extraction desulfurization. This process has certain limitations. It can only remove inorganic sulfur and low-carbon mercaptans, while for other organic sulfur such as carbonyl The desulfurization effect of sulfur, thiophene sulfur, etc. is not good, so it is difficult to desulfurize the carbon-penta-conjugated diene raw materials to less than 10ppm

[0006] The existing single desulfurization process cannot remove various sulfides at the same time, and often requires the combined use of several desulfurization methods

And there are deficiencies in these desulfurization methods: first of all, whether it is alcohol amine refining, Merox extraction-liquid phase catalytic oxidation desulfurization, when the total sulfur content in the feed gas is high, the desulfurization effect is not good, and in Merox extraction- The catalyst used in the liquid-phase catalytic oxidation method is easy to deactivate; in addition, the existing method has a good effect on the treatment of inorganic sulfur, but the effect of removing organic sulfur is poor, especially for organic sulfur compounds with large molecular weight, such as mercaptans. , sulfide, thiophene, etc., the effect is very poor; in addition, the existing method also has the problem that the waste liquid and waste residue are difficult to handle

The preparation method of the impregnation solution disclosed in U.S. Patent No. 4,913,802 is to add cobalt phthalocyanine compounds in 2% ammonia water and 1% quaternary ammonium alkali mixed solution, although the conversion of cobalt phthalocyanine compounds to inactive components can be slowed down, However, the bed catalyst prepared with this impregnation solution is easy to lose during the deodorization process. On the one hand, it is not friendly to the environment and is easy to cause pollution. On the other hand, it will lead to a shorter service life of the bed.

The oxidative deodorization and desulfurization method described in the domestic patent No. CN101063042A uses heteropolyacids and heteropolyacids as homogeneous catalysts to react in high-efficiency mass transfer reactors with enhanced turbulent internals to obtain odorless high-quality oil products , but the disadvantage of this method is that it cannot remove thiophene sulfur and its derivatives, so it cannot be used in the ultra-deep desulfurization of C5-conjugated diene raw materials

[0008] To sum up, in the existing literature or patents, the ultra-deep desulfurization of C5 raw materials is still a blank; the existing sulfide removal technology in olefins also has some challenging problems, such as: 1. The desulfurization depth is not enough , it is difficult to remove thiophene sulfur, so it is difficult to remove sulfur from 50-200ppm to less than 10ppm; 2. The desulfurization process consumes a lot of energy, the operating conditions are harsh, and the operating cost is high; 3. The desulfurization process is not friendly to the environment