A kind of preparation method of sulfurized reforming catalyst

Abstract

The invention relates to a preparation method of a sulfurized state reforming catalyst, and the preparation method comprises the following steps of: replacing a reactor filled with an oxidation state reforming catalyst with an inert gas, and then accessing hydrogen which contains hydrogen sulfide; and then increasing the temperature of a catalyst bed layer into 450-550 DEG C at the temperature increasing rate of 20-80 DEG C / hour for constant temperature treatment so as to obtain the sulfurized state reforming catalyst. The sulfurized state reforming catalyst comprises a high-temperature resistant inorganic oxide carrier and the following components with content in percentage by weight: 0.05%-2.0% of platinum metal, 0.05%-2.0% of VIIB metal, 0.05%-5.0% of halogens and 0.15%-0.3% of sulfur, wherein the components are computed by taking the high-temperature resistant inorganic oxide carrier as a reference; and the mass ratio of the sulfur content and theoretical sulfur content of the sulfurized state reforming catalyst is 1.8-3.0. The method disclosed by the invention can be used for carrying out reduction and presulfurization on the oxidation state catalyst by directly using the hydrogen which contains the hydrogen sulfide; and the prepared sulfurized state reforming catalyst has the advantages of higher reaction activity and aromatic hydrocarbon selectivity.

Description

technical field

[0001] The invention is a method for preparing a naphtha reforming catalyst, in particular, a method for preparing a sulfided reforming catalyst used in a semi-regenerative reforming unit. Background technique

[0002] Catalytic reforming is a process for producing high-octane gasoline blending components or producing light aromatics (benzene, toluene, xylene) as important petrochemical raw materials and providing cheap hydrogen. In recent years, with the increasingly stringent environmental protection requirements, the rapid development of the polyester industry, the increasing demand for hydrogen and the continuous improvement of oil quality requirements in the oil refining industry, the production capacity of catalytic reforming units has increased year by year, of which semi-regenerative Reformers occupy a very important position.

[0003] Semi-regenerative reforming catalysts are mainly platinum-rhenium catalysts, which need to be dried, activated, redu...

Examples

example 1

[0023] (1) Preparation of oxidation state catalyst

[0024] Take 50 grams of γ-Al 2 o 3The carrier is prepared with chloroplatinic acid, perrhenic acid and hydrochloric acid to form an impregnation solution, so that the liquid / solid volume ratio is 1.3, and the impregnation solution contains 0.22 mass % of platinum, 0.46 mass % of rhenium and 1.5 mass % of chlorine (all relative to dry basis Aluminum oxide calculation). First place the carrier in a reduced-pressure environment, make the pressure reach 0.02MPa, and maintain it for 0.5 hours, stop the decompression operation, introduce the impregnating solution, rotate and impregnate at 30°C for 3 hours, and then spin-dry at 60°C and 0.02MPa for 1 hour. The solid was taken out and dried at 120°C for 12 hours, then calcined with dry air at 500°C and the gas / solid volume ratio was 700 for 4 hours to obtain an oxidized catalyst.

[0025] (2) Preparation of sulfurized catalyst

[0026] Put the catalyst in the oxidized state into...

example 2

[0028] The method for preparing sulfided state catalyst by the example 1, difference is (2) step feeds the hydrogen that hydrogen sulfide content is 0.1mL / L in the reactor, make gas / solid volume ratio be 1000, press the speed of 30 ℃ / hour The temperature of the catalyst bed was raised to 460° C. and kept at this temperature for 2 hours. Then the temperature of the catalyst bed was lowered to 25° C., changed to nitrogen, purged for 0.5 hour, and the catalyst was unloaded and sealed for storage. The composition of the prepared sulfided catalyst B is shown in Table 1.

example 3

[0030] The method for preparing sulfide state catalyst by example 1, difference is (2) step feeds the hydrogen that hydrogen sulfide content is 2mL / L in the reactor, make gas / solid volume ratio be 600, by the rate of 50 DEG C / hour The temperature of the catalyst bed was raised to 460° C. and kept at this temperature for 2 hours. Then the temperature of the catalyst bed was lowered to 25° C., changed to nitrogen, purged for 0.5 hour, and the catalyst was unloaded and sealed for storage. The composition of the obtained sulfided catalyst C is shown in Table 1.

technical field

[0001] The invention is a method for preparing a naphtha reforming catalyst, in particular, a method for preparing a sulfided reforming catalyst used in a semi-regenerative reforming unit. Background technique

[0002] Catalytic reforming is a process for producing high-octane gasoline blending components or producing light aromatics (benzene, toluene, xylene) as important petrochemical raw materials and providing cheap hydrogen. In recent years, with the increasingly stringent environmental protection requirements, the rapid development of the polyester industry, the increasing demand for hydrogen and the continuous improvement of oil quality requirements in the oil refining industry, the production capacity of catalytic reforming units has increased year by year, of which semi-regenerative Reformers occupy a very important position.

[0003] Semi-regenerative reforming catalysts are mainly platinum-rhenium catalysts, which need to be dried, activated, redu...

Examples

example 1

[0023] (1) Preparation of oxidation state catalyst

[0024] Take 50 grams of γ-Al 2 o 3The carrier is prepared with chloroplatinic acid, perrhenic acid and hydrochloric acid to form an impregnation solution, so that the liquid / solid volume ratio is 1.3, and the impregnation solution contains 0.22 mass % of platinum, 0.46 mass % of rhenium and 1.5 mass % of chlorine (all relative to dry basis Aluminum oxide calculation). First place the carrier in a reduced-pressure environment, make the pressure reach 0.02MPa, and maintain it for 0.5 hours, stop the decompression operation, introduce the impregnating solution, rotate and impregnate at 30°C for 3 hours, and then spin-dry at 60°C and 0.02MPa for 1 hour. The solid was taken out and dried at 120°C for 12 hours, then calcined with dry air at 500°C and the gas / solid volume ratio was 700 for 4 hours to obtain an oxidized catalyst.

[0025] (2) Preparation of sulfurized catalyst

[0026] Put the catalyst in the oxidized state into...

example 2

[0028] The method for preparing sulfided state catalyst by the example 1, difference is (2) step feeds the hydrogen that hydrogen sulfide content is 0.1mL / L in the reactor, make gas / solid volume ratio be 1000, press the speed of 30 ℃ / hour The temperature of the catalyst bed was raised to 460° C. and kept at this temperature for 2 hours. Then the temperature of the catalyst bed was lowered to 25° C., changed to nitrogen, purged for 0.5 hour, and the catalyst was unloaded and sealed for storage. The composition of the prepared sulfided catalyst B is shown in Table 1.

example 3

[0030] The method for preparing sulfide state catalyst by example 1, difference is (2) step feeds the hydrogen that hydrogen sulfide content is 2mL / L in the reactor, make gas / solid volume ratio be 600, by the rate of 50 DEG C / hour The temperature of the catalyst bed was raised to 460° C. and kept at this temperature for 2 hours. Then the temperature of the catalyst bed was lowered to 25° C., changed to nitrogen, purged for 0.5 hour, and the catalyst was unloaded and sealed for storage. The composition of the obtained sulfided catalyst C is shown in Table 1.

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