Preparation method of gasoline desulfurization microsphere catalyst

Abstract

The invention relates to a preparation method of a gasoline desulfurization microsphere catalyst. The method is characterized by: adding activated zinc oxide accounting for 30-60wt% of the total dry basis of the catalyst, expanded perlite powder and / or diatomite accounting for 5-20wt% of total dry basis, and a nickel salt, in terms of nickel oxide, accounting for 10-30wt% of the total dry basis into chemical water for mixing and beating, and raising the temperature to 60-90DEG C, at the same time continuously adding a sodium aluminate solution and an aluminum sulfate solution with a concentration of 1-20 wt%, adjusting and controlling the flow ratio of the two solutions to maintain the pH of the whole slurry at 7.5-9.5; and with the total amount of alumina in the sodium aluminate and aluminum sulfate accounting for 5-20wt% of the total dry basis of the catalyst, atomizing the uniformly mixed material slurry into microspheres with an average particle diameter of 50-80 microns, then conducting washing with chemical water till sodium oxide is less than 1.0wt%, and after drying, carrying out roasting at a temperature of 450-650DEG C for 0.5-4 hours. The prepared catalyst has a pore volume of 0.1-0.4 ml / g, and is characterized by good strength, high activity, large sulfur capacity, as well as low loss of liquid yield and gasoline octane number in a gasoline desulfurization reaction.

Description

technical field [0001] The invention relates to a method for preparing a microsphere catalyst for gasoline desulfurization, more specifically to a method for preparing a microsphere catalyst for hydrogen adsorption desulfurization under gasoline fluidization conditions. Background technique [0002] In recent years, many countries in the world have made strict regulations on the sulfur content of motor gasoline through regulations, requiring the production and use of environmentally friendly ultra-low sulfur gasoline. Deep desulfurization of gasoline has become a major challenge for my country's oil refining industry. Using a hydrogenation process such as that described in USP 20100300932, hydrodesulfurization of gasoline is a common method. However, for FCC gasoline with high olefin content, there is no mature hydrogenation process technology that can be used to produce ultra-low sulfur clean gasoline with a sulfur content of less than 10 μg / g. [0003] Among gasoline dee...

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Problems solved by technology

CN101433821A, CN101434854A, CN101434862A, CN1261218C, CN1583972A, CN1583973A disclose the method of cracking and desulfurization under the condition of non-hydrogen-containing zeolite desulfurizer, but the desulfurization rate can only reach 50-80% by weight generally, and cannot be used to produce oil products with low sulfur content , and the loss of gasoline liquid is relatively large

CN1952049A discloses a metal-containing active carbon gasoline and diesel adsorption desulfurizer and its preparation method. Although this type of adsorbent has certain adsorption and desulfurization capabilities, it is basically unable to obtain low-sulfur product fuel oil

[0004] It is mentioned in USP6221280 that skeleton nickel can be used as an adsorbent to remove thiophene sulfur remaining in hydrocarbon fuel after hydrodesulfurization, and CN1407064A discloses a method for desulfurizing using a nickel-based amorphous alloy adsorbent in a slurry bed, and the desulfurization rate can reach 60 % by weight, but this kind of adsorbent has poor regenerability and cannot be used for continuous regeneration

CN1406914A is to use nickel base amorphous alloy adsorbent to remove C in the slurry bed 6 ~C 11 In the method of sulfide in aromatic hydrocarbons, the sulfur content can be reduced to below 0.05 μg / g, and the disadvantages are the same, that is, the adsorbent has poor regenerability and cannot be continuously regenerated, which actually limits its use.

CN1110931A, CN1151333A adopt the adsorbent of zinc oxide, silicon oxide, colloidal oxide and accelerator, and add inflammable pore-forming agent when heating in colloid to improve its pore volume, but can reduce the intensity of adsorbent

CN101618314A introduces layered clay into the adsorbent for improvement, because the acidic active center of layered clay is easy to deposit carbon and reduce liquid absorption, which also limits its practical use

CN101619231A uses a complexing agent to improve the carrier and tries to increase the pore volume through dealumination, but it is found that its performance cannot be improved during use

CN1208124C and CN1627988A disclose adopting the precursor impregnation of nickel to be impregnated by the adsorbent carrier of zinc oxide, expanded perlite and alumina, for desulfurization from cracked gasoline and diesel fuel, but the strength of adsorbent is not good enough in use high

The improvement of CN101618313A is mainly to use nickel tetracarbonyl as an active component to reduce the amount of nickel, but the toxicity of nickel tetracarbonyl brings inconvenience to the production process and limits its practical use

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