KR101469814B1 - Method for manufacture catalyst material from desulfurization waste catalyst of an oil refinery - Google Patents

Abstract

The present invention relates to a process for the purification of crude oil, which comprises using a waste catalyst dissolved in an alkali or acid, diluting it with water, making an acidic solution, adding monooxylamine to the vanadium first, adding soda ash or methyl acetate, , And methyl ethanol to solidify the metal components, precipitate the precipitates, wash them with water, and oxidize them by a heating method. Thus, a metal oxide mixed with nickel oxide, cobalt oxide, molybdenum oxide and aluminum oxide can be obtained and used as a catalyst material .

Spent catalyst, vanadium, mono-oxyamine, spent catalyst

Description

METHOD FOR MANUFACTURE CATALYST MATERIAL FROM DESULFURIZATION WASTE CATALYST OF AN OIL REFINERY BACKGROUND OF THE INVENTION [0001]

The present invention relates to a production method which can be used in a factory for refining crude oil and to use a waste catalyst whose lifetime is abandoned as a catalyst material.

The waste catalyst used in refineries contains considerable amounts of waste oil, silicon, carbon, molybdenum, vanadium, nickel, cobalt, aluminum tungsten, etc. In the present invention, vanadium, which occupies a large portion of the mixed materials, Thereby making the material into an oxide to be used as a catalyst raw material.

Conventionally, a technique for separating vanadium or molybdenum from waste catalysts has been developed. However, this technique has the inconvenience that vanadium or molybdenum mixed in the waste catalyst is recovered and the remaining metal components are discarded, which is not economical.

The present invention has been made in order to improve the above-mentioned points and to separate the vanadium mixed in the spent catalyst before the use of the spent catalyst, and to make the remaining metal material into an oxide to form an oxide mixture, This can help to increase the utilization of waste and solve the cause of environmental pollution.

 The invention is used in an oil refinery to remove sulfur and oil by using a known de-rusting catalyst, and the spent catalyst is reacted with an alkali or acid to dissolve the metal component, which is then filtered to remove the vanadium first, Component is made into an oxide and used as a catalyst raw material.

To this end, the present invention is characterized in that caustic soda is mixed with caustic soda in a ratio of 1: 3 by weight to a waste catalyst from which sulfur and oil have been removed, and the mixture is heated and stirred at 135 ° C to obtain a reaction product. The reaction product is diluted with water and filtered, and sulfuric acid or hydrochloric acid is added 2, and mono-octylamine (CH ₃ (CH ₂ ) ₇ NH ₂ ) was added thereto, followed by stirring at 50 to 90 ° C for 2 to 3 hours to precipitate the vanadium component as a solid. The filtrate was filtered to remove vanadium First,

Vanadium was separated from the filtrate by adding concentrated soda ash to maintain the pH between 7 and 8. The mixture was heated to 50 ~ 90 ℃ and agitated for 2 ~ 3 hours to change the metal materials in the filtrate into carbonate mixture. A step of preparing a powdery carbonate mixture in which moisture and salt are removed, and

The carbonate mixture in powder form is heated to 150 to 360 ° C to remove the carbonic acid gas to convert the molten carbonate to a mixed oxide in which molybdenum oxide, aluminum oxide, nickel oxide, cobalt oxide and tungsten are mixed at a certain ratio.

In addition, the present invention relates to a method for preparing a catalyst composition, which comprises mixing a de-rusting catalyst with a concentrated sulfuric acid (97%) solution at a weight ratio of 1: 3, heating the mixture at 260 캜 for 30 minutes, diluting the mixture with 8 to 9 times of water, Then, mono-oxylamine is added to the filtrate, and the resulting vanadium is separated by stirring sufficiently. The filtrate from which the vanadium is separated is taken out, and one or two solvents selected from among methyl acetate, acetone and methyl ethanol are added to solidify the metal component The solid obtained by precipitation and filtration is heated to 150 to 480 캜 to obtain a metal oxide present in a mixed state of aluminum oxide, molybdenum oxide, nickel oxide, and cobalt oxide, and to use it as a catalyst raw material.

Example (1)

300 g of caustic soda (300 g) was added to 100 g of de-rusted catalyst from which sulfur and oil had been removed. The reaction mixture was heated at 135 ° C and diluted with water. The resulting solution was filtered and concentrated to a pH of 1 to 2 by adding concentrated sulfuric acid (97% And the resulting filtrate was taken out of the supernatant liquid. The resulting filtrate was added to a concentrated soda ash solution to agitate the mixture at pH 7.5 for 2 hours. After that, a carbonate solid was produced, and a carbonate solid was produced The solution was vacuum-concentrated, dried and then washed with water or a carbonate solid, and the filtrate was heated at 150 ° C. for 40 minutes to obtain 60 g of an oxide mixed with 35 g of aluminum oxide, 14 g of molybdenum oxide, 4 g of cobalt oxide and 7 g of nickel oxide.

Example (2)

(100 g) was added to 300 g of sulfuric acid (97%). The mixture was heated at 260 DEG C for 30 minutes, 800 g of water was added and stirred at 90 DEG C for 40 minutes. 55 g of monooxylamine was added to the filtrate, And the remaining filtrate was added with 500 g of methyl acetate to obtain a precipitate. The mixture was heated to 360 DEG C to obtain 64 g of an oxide mixed with 16 g of molybdenum oxide, 5 g of nickel oxide, 4 g of cobalt oxide and 39 g of aluminum oxide.

Example (3)

100 g of waste catalyst was added to 300 g of sulfuric acid (97%). The mixture was heated at 260 DEG C for 30 minutes, 800 g of water was added and stirred at 90 DEG C for 40 minutes. Then 55 g of monooxylamine was added to the filtrate, The mixture was heated to 480 ° C and 65 g of a mixture of 16 g of molybdenum oxide, 5 g of nickel oxide, 4 g of cobalt oxide, 39 g of aluminum oxide and 1.0 g of tungsten oxide was added to the filtrate. .

According to the present invention as described above, caustic soda is added to a spent catalyst to dissolve a metal component, which is then alkalized and diluted with water. The filtrate is filtrated with hydrochloric acid or sulfuric acid to obtain a hydrochloride or sulfate mixture, which is diluted with water, and an organic monooxylamine To remove the vanadium. Thus, the filtrate from which the vanadium is removed is solidified. The filtrate is washed with water to remove salt, and then heated and dried to obtain an oxide mixture. Thus, a catalyst material can be prepared.

In addition, the waste catalyst was reacted with concentrated sulfuric acid (97%) instead of caustic soda to dissolve metal components, and an acidic filtrate was obtained. Monooxyamine was added to the filtrate to separate the vanadium. Solvents were added to the remaining filtrate to obtain a solid Since the treated product obtained by mixing the metal oxides can be obtained by post-heating treatment, it can be used for the raw material for the catalyst preparation, thereby obtaining an advantage that the resource conversion ratio of the waste can be increased.

Claims (6)

delete The deaerated catalyst was heated to 400 to 600 ° C to remove sulfur and oil, and the remaining catalyst was mixed with caustic soda in a ratio of 1: 3 wt%. The reaction mixture was heated and stirred at 135 ° C to obtain a reaction product, which was diluted with water, Sulfuric acid or hydrochloric acid is added to maintain the pH at 1 to 2, mono-octylamine (CH ₃ (CH ₂ ) ₇ NH ₂ ) is added thereto and stirred at 50 to 90 ° C for 2 to 3 hours to precipitate the vanadium component as a solid Filtering the filtrate to separate the vanadium, The filtrate from which the vanadium was separated was added to the concentrated soda ash solution, heated to 50 to 90 캜 while maintaining the pH of 7 to 8, and aged for 2 to 3 hours to solidify the metal materials in the filtrate by changing into a carbonate mixture. A step of preparing a powdery carbonate mixture in which water and salt are removed, and The carbonate carbonate powder mixture is heated to 150 to 380 ° C to remove the carbonic acid gas to convert it into a mixed oxide in which molybdenum oxide, aluminum oxide, nickel oxide, and cobalt oxide are mixed at a certain ratio, Of preparing a mixed catalyst material in a catalyst The deaerated catalyst was mixed with concentrated sulfuric acid (97%) at a weight ratio of 1: 3 and reacted by heating at 260 DEG C for 30 minutes. Water corresponding to 8 to 9 times the weight of the reactant was added thereto, stirred at 90 DEG C for 40 minutes, Mono-oxylamine is added to the filtrate, and the resulting vanadium is separated by stirring. One or two solvents selected from among methyl acetate, acetone, and methyl ethanol are added to the remaining solution to solidify the metal components, A method for producing a mixed catalyst raw material in an oil refinery de-rusting catalyst which can obtain an oxide present in a mixed state of aluminum oxide, molybdenum oxide, nickel oxide, and cobalt oxide by heating a solid at 150 to 360 ° C to use as a catalyst raw material A method for producing a mixed catalyst raw material in an oil refinery catalyst of refinery in which the solvent in the above 3 is methyl acetate The process according to claim 3, wherein the solvent is acetone. The process according to claim 3, wherein the solvent is methyl ethanol.