The preparation method of catalyst for hydrotreating petroleum fractions

 

(57) Abstract:

The invention relates to petrochemistry and oil refining, more specifically, to the manufacture of catalysts for Hydrotreating petroleum fractions. A method for preparing a catalyst for Hydrotreating petroleum fractions, including separate precipitation of sodium aluminate acid at room temperature and boiling, the subsequent mixing of the received modifications of aluminum hydroxide hot and cold deposition at a mass ratio of 3:1-1:2, flushing, forming hydroxide or/and made of alumina powder with addition of 0.5-12 % kaolin, drying and calcining the carrier and the application to it of Nickel or cobalt and molybdenum impregnated with a solution of compounds of these metals, drying and calcination of the obtained catalyst when 220-420oC. Method allows to obtain a catalyst with high obestsenivaya and diasterous activity and strength. 1 S. and 2 C.p. f-crystals, 4 PL.

The invention relates to the production of catalysts for Hydrotreating petroleum fractions and can be used in the refining and petrochemical industries.

Catalysts for Hydrotreating petroleum fractions used in purification processes oside (NiO, CoO, MoO3). In most cases, the carrier of the catalyst is active gamma-alumina /1/, and also a mixture of different forms oxide: gamma-, ETA -, and amorphous /2/.

A known method of preparation of Hydrotreating catalysts by impregnation of alumina with solutions of compounds active ingredients (compounds of Nickel, cobalt, molybdenum), followed by drying and calcining /1-3/. In some cases, the catalyst composition is injected additives other ingredients: silica /1/, p /4/ titanium /5/. Impregnating method of preparing catalysts is relatively complex, it results in catalysts with good obestsenivaya, but reduced diasterous activity.

The closest in technical essence to the proposed method of preparation of the catalyst Hydrotreating is the method described in the prototype /6/. This method consists of the following main stages: deposition of sodium aluminate acid at room temperature and the boiling, the subsequent mixing of modifications of aluminum hydroxide, hot and cold deposition in the ratio of 1: 1, wash the precipitate of aluminum hydroxide from harmful impurities, impregnation suspension of aluminium hydroxide solutions of ammonium molybdate the catalyst.

The known method is characterized by the simplicity of the technology, but the resulting catalysts have low activity.

The purpose of the invention is to increase the activity of the catalyst Hydrotreating.

The goal was achieved by the method of preparation of the catalyst, also including separate precipitation of sodium aluminate acid at room temperature and the boiling, the subsequent mixing of modifications of aluminum hydroxide, hot and cold precipitation, stage, washing the precipitate, aluminum hydroxide impregnation with a solution of compounds of molybdenum, Nickel or cobalt, forming, drying and calcination of the catalyst with the difference that the molding is subjected to the aluminum hydroxide and/or alumina powder in a mixture with 0.5 to 12 kaolin, dried and calcined received media and provides its impregnation with a solution of compounds of these metals.

Salient features of the claimed method are:

the molding is subjected to a hydroxide and/or alumina powder mixed with kaolin;

the content of the kaolin in the mixture before forming 0.5 to 12 per calcined carrier;

dried and calcined received media;

carry out the impregnation of the calcined h is Aligator on the proposed method are:

a mixture of modifications hydroxides hot and cold deposition, including, to obtain a powder of aluminum oxide in a mass ratio of 3:1-1:2.

the temperature of calcination of the catalyst 220-420oC.

The proposed method of preparation of Hydrotreating catalysts is as follows. Deposition of nitric acid from sodium aluminate solution at room temperature and the boiling receive a modification of aluminum hydroxide, hot and cold precipitation. They are mixed in a mass ratio of 3:1-1: 2. After washing from sodium ions pellet or powder of aluminum hydroxide in the kneading machine is mixed with the specified amount of kaolin, add the required amount of patinator nitric acid and, if necessary, water and formed into a screw extruder.

In another case, aluminum hydroxide, calcined in air at 400-600oC and get an alumina powder, which is mixed with the kaolin with the addition of patinator water and then subjected to molding.

It is also possible to mould a mixture of hydroxide, alumina and kaolin.

The plant is convenient to obtain a powder of aluminum oxide with the formation of hydroxide to obtain extrudates, which is what the op.

If you want to enter in the composition of the catalyst, the phosphorus mixture before forming Pentateuch phosphoric acid instead of nitric.

Carriers dried at 30-120 oC and calcined in a stream of dry air at a temperature of 400-600 oC.

You can use a solution containing, in addition to ammonium molybdate, Nickel and cobalt at the same time. After impregnation the catalyst is dried and then calcined in a stream of air at temperatures between 200 and 600 oC, preferably at 220-420oC. the Active components can be partially paid at the stage of the dough before forming. In this case, the rest of them introduced by impregnation of the calcined carrier.

Proposed method are the catalyst with high obestsenivaya and diasterous activity. So, the rest of the nitrogen content after Hydrotreating catalyst prepared by the proposed method, 1.2-3 times lower, and sulfur 2.0-3 times lower than the known catalyst. The mechanical strength of the catalyst for the split does not yield obtained in a known manner.

The set of distinctive features of the proposed method meets the criterion of novelty.

According to the method of preparation of the catalyst charge agains the group of 3:1-1:2 get more active catalysts, than prepared by a known method.

Thus, the proposed solution meets the criterion of non-obviousness.

Example 1. Prepare aluminumalloy catalyst containing 2,9 NiO and 15 MoO3aluminum oxide obtained by mixing the modifications of hydroxides of aluminum, hot and cold deposition in the ratio of 1:1, with the introduction of a batch of 20 of aluminum oxide and 0.5 kaolin. Cold precipitation. In the reactor, which is 0,72 l of water, at the same time drained for 2-3 h 0,396 l of sodium aluminate (concentration in terms of 150 g/l of caustic module 1,7) and 0.312 g of nitric acid (concentration 756 g/l). The reaction is carried out at intensive stirring and cooling (through the coil in the editor keep the temperature 18-22oC). The pH value of the suspension is maintained within the range of 9.2 to 9.5, by changing the speed of discharge of nitric acid. After deposition of conducting stabilization of aluminum hydroxide by boiling the suspension for 1 h Receive 1.56 kg suspension containing and 82.2 g of aluminum hydroxide (pseudoboehmite), it is in terms of Al2O360 g of the Suspension of cold and hot deposition are mixed in a ratio of 1:1 (for other examples in a predetermined ratio), and serves on the filter, where the Department is C from sodium ions. Part of the aluminum hydroxide formed by using a screw extruder. The extrudates are dried at a temperature of 100-110oC and then calcined in a stream of dry air to a temperature of 550oC. Calcined alumina milled on a ball mill to obtain a powder fraction less than 120 μm. The aluminum hydroxide-modified hot and cold deposition of 1:1 in the number of 79.5 g (based on the calcined sample) are mixed in a kneading machine with 20 g of alumina powder and 0.5 g of kaolin. Use "enriched kaolin for rubber and plastic products, artificial leather and fabrics" brand MCT according to GOST 19608-84. The mixture was added for peptization 0.6 g of nitric acid (concentration of 750 g/l). The plastic mass is subjected to molding by extrusion in a screw machine. The extrudates are dried at 110oC for 10 h, and then calcined at 550oC in a stream of dry air for 4 hours, 100 g of the obtained carrier is impregnated with 75 ml of ammonia solution containing 22,0 g of ammonium molybdate and 13.4 g of Nickel nitrate (Ni(NO3)26H2). The media stand in the solution for 1 h at room temperature and stirring, the catalyst is dried at 50-130oC and calcined in a stream of dry air at 500oC for 4 is split according to OST 3801130-77, 2.4 kg/mm, the Catalyst was tested in the process of Hydrotreating a diesel oils wikipeida within 200-360oC containing 0,95 sulfur and 0,0113 nitrogen. Test conditions: temperature 380oC, a pressure of 4 MPa, the space velocity of the feed 6 h-1the ratio of hydrogen/feedstock 500 nl/l Before the test catalyst sarnaut raw material at temperatures 150-260 oC. under these conditions, the residual content of sulfur and nitrogen was 0.009 and 0,0024 the Results are given in table. 2.

Poker 2. Prepare a catalyst similar to the method described in example 1 with the difference that the content of aluminum oxide in the mixture before molding is 40 kaolin 1 and the temperature of calcination of the catalyst is 300oC. the strength Factor split 2.1 kg/mm characteristics of the catalyst are given in table. 1. The catalyst was tested raw material and under the conditions of example 1. The residual content of sulfur and nitrogen in the hydrotreated product, respectively 0,0055 and 0,0022

Example 3. The catalyst is prepared analogously to example 2, but the temperature of calcination of the catalyst is 420oC. characteristics of the catalyst are the same as in example 2. The residual content of sulfur and azote in the hydrotreated product 0,007 and 0,0038 is utilizator similar to example 1, but the temperature of annealing 220oC. to a Residual content of sulfur and nitrogen in the hydrotreated product is accordingly 0,0072 and 0,0055

Example 5. The composition and method of preparation of the catalyst is similar to described in example 2, but the temperature of annealing is 500oC. characteristics of the catalyst is the same as in example 2. The residual content of sulfur and nitrogen in the test conditions given in example 2, respectively 0,0083 and 0,0055 the Results shown in examples 2-5 illustrate a preferred range of temperature of calcination of the catalyst, comprising 220-420oC. Annealing at temperatures below 220oC is impractical, because these conditions are not fully decomposed ammonia complex of active ingredients, so in conditions of Hydrotreating possible allocation of nitrogen oxides, which is unfavorable from the viewpoint of corrosion of the equipment.

Example 6. Prepare the catalyst according to example 2 with the difference that the molding is subjected to a mixture of aluminum hydroxide with kaolin without the addition of aluminum oxide. The strength factor of the catalyst 2.2 kg/ml characteristics of the catalyst are given in table. 1. The catalyst was tested under the conditions islogin,0060 the Results are given in table. 2.

Example 7. Prepare a catalyst having a content of active ingredients, as in example 1 and calcined at the same temperature 500oC. However, the catalyst carrier containing 90 aluminum oxide and 10 kaolin, prepared as follows. 90 g of alumina powder obtained analogously to example 1, are mixed in a kneading machine with the addition of 10 g of kaolin and add 1.8 g of nitric acid. The plastic mass is formed on the screw extrudate. The next stage of preparation of the catalyst is similar to example 1. The strength factor of the catalyst 2.7 kg/mm characteristic described in the table. 1. The catalyst was tested under the conditions set forth in example 1. The residual content of sulfur and nitrogen in the hydrotreated product is 0,0063 and 0,0053 respectively. The results are shown in table. 2.

Example 8 (comparative). The catalyst is prepared analogously to example 7 with the difference that the molding does not add kaolin. The strength factor of the catalyst 1.2 kg/mm Characteristics are given in table. 1. The catalyst was tested under the conditions of example 1. The residual content of sulfur and nitrogen in the product 0,008 Results are given in table. 2. In the absence of kaolin is not achieved high strength of the catalyst is about the ratio of modifications of hot and cold deposition is taken in a ratio of 3:1, and the amount of the kaolin take based on 12 calcined carrier. The catalyst pierce at a temperature of 300oC. the strength Factor of the catalyst 2.7 kg/mm characteristics of the catalyst are given in table. 1. The residual content of sulfur and nitrogen in the hydrotreated product is 0.009 and 0,0065 respectively. The results are given in table. 2. The example illustrates the upper redistribution in the ratio of modification of hydroxides of aluminum, hot and cold deposition, the content of the kaolin in the media, even when achieved increased activity when diazotoluene diesel fuel.

Example 10. Prepare the catalyst as in example 1 with the difference that the ratio of modifications hydroxide, hot and cold deposition is 1:2, and the content of the kaolin in the media is 5, the Catalyst was calcined at a temperature of 300oC. the strength Factor split is 1.8 kg/mm characteristics of the catalysts are given in table. 1. The catalyst was tested under the conditions of example 2. The content of sulfur and nitrogen in the hydrotreated product is accordingly 0,0083 and 0,0067 Example illustrates the lower limit of the ratio of the modifications of hot and cold deposition is achieved when polychaete hydroxides of aluminum, hot and cold deposition in the ratio by weight of 1:1, scrub the mixture on the filter according to example 1. Get the aluminum hydroxide, the amount of which in terms of aluminum oxide 120, Impregnated with aluminum hydroxide solutions of ammonium molybdate and Nickel nitrate, respectively take of 26.4 g of ammonium molybdate and 16.1 g of Nickel nitrate. After mixing, the excess solution is sucked off on a vacuum filter. The plastic mass is formed in a screw extrusion machine. Dried at 50-130oC 10 h and then calcined at 500oC in a stream of dry air for 4 hours, the Composition of the Nickel-molybdenum and its strength are presented in table. 1. The catalyst was tested under the conditions of example 1. The content of sulfur and nitrogen in the hydrotreated product, respectively 0,0185 and 0,0085

Example 12 (prototype cf.) the Catalyst is prepared analogously to example 11, but the temperature of calcination of the catalyst is 300oC. the strength Factor of the catalyst is not changed (table.1). The catalyst was tested under the conditions of example 1. The content of sulfur and nitrogen in the hydrotreated product is 0,016 and 0,0080 the Results are given in table. 2. They show that by reducing the temperature of calcination of the catalyst prepared according to the prototype, the catalyst activity increases with decreasing tempera is the outer coat of the catalyst is lower than cooked proposed in the present invention method.

When comparing results on Hydrotreating catalysts prepared by the proposed method (examples 1-7, 9, 10) with the results of examples 11 and 12 shows that the proposed method gives the catalysts with increased strength, diasterous and obestsenivaya activity.

Example 13. Aluminumalloy the catalyst prepared using the medium described in example 2, i.e., the ratio of modifications hydroxides hot and cold deposition of 1:1, adding a powder of aluminum oxide 40 kaolin 1 However, unlike example 2, in a kneading machine prior to forming impose a 30 salts of active ingredients. 100 g of the mixture in the calculation of the calcined sample is injected 4.5 g of nitrate Nickel and 7.3 g of ammonium molybdate. After shaping, drying at 50oC and 110oC and calcining in a stream of air at 500oC for 4 h, the carrier is impregnated with ammonium solution containing a 8.9 g of salt of Nickel nitrate and 14.7 salt of ammonium molybdate, about 70 of the total number of active components. The catalyst was dried at 50-130oC and then calcined at a temperature of 300oC. the strength Factor of the catalyst 2.2 kg/mm, the Catalyst was tested at uslaw the possibility of introducing a part of the active components at the stage of preparation of the carrier prior to moulding.

Example 14. Prepare allocability the catalyst by impregnating 100 g of aluminum oxide obtained by mixing hot and cold modifications of aluminum hydroxide with a mass ratio of 3:1, the addition of 40 powder of aluminum oxide and 12 of kaolin in a kneading machine prior to moulding. The carrier is calcined in a stream of dry air at 550 oC for 4 h the resulting carrier is impregnated with 76 ml of ammonia solution containing of 21.6 g of ammonium molybdate and 11.4 of cobalt nitrate. The catalyst is kept in the solution for 1 h and then dried at 60 to 90oC 6 h and 3 h at 130oC. the Catalyst was calcined in air flow at 550oC. the strength Factor of the catalyst 2.7 kg/mm characteristics of the catalyst are given in table. 1. The catalyst was tested under the conditions described in example 1. The content of sulfur and nitrogen in the hydrotreated product 0,0082 and 0,0068 respectively. The test results are given in table. 2.

Example 15. Prepare allocability catalyst, similar to that described in example 14, with the difference that the ratio of modifications of hot and cold deposition taken in the ratio 1:2, the mixture was added 0.5 kaolin. The catalyst contains 2.5 CoO and 15 MoO3. The strength factor of the catalyst 1.9 kg/mm, Although in the hydrotreated product 0,0077 and 0,0081 respectively. The results are given in table. 2.

Example 16 (the prototype). Prepare a catalyst similar to that described in example 1 with the difference that instead of Nickel nitrate use nitrate of cobalt in the amount of 13.7, Get allocable molybdenum catalyst, the characteristics of which are presented in table.1. The catalyst was tested under the conditions of example 1. The content of sulfur and nitrogen in the hydrotreated product 0,0196 and 0.01

Example 17. Prepare the catalyst as in example 1 with the difference that instead of nitric acid as peptizing agent used ortho-phosphoric acid at the rate of 3 g H3PO4100 g of calcined carrier. The catalyst contains 2.1 P2O5. The strength factor of the catalyst 2.5 kg/mm characteristics of the catalyst are given in table. 1. The catalyst was tested under the conditions of example 1. The content of sulfur and nitrogen in the hydrotreated product 0,0078 and 0,0024 the test Result is shown in table. 2.

Example 18. The catalyst is prepared analogously to example 1 with the difference that the mixture before forming media add silicasol based introduction 7 SiO2from the mass media. The catalyst contains a 5.5 SiO2and has a safety factor of 2.3 kg/mm Features and advantages of the hydrotreated product 0,0065 and 0,0033 respectively. The results are given in table. 2. Examples 17 and 18 illustrate the suitability of the proposed method for preparation of the catalyst Hydrotreating and if they contain known promoting additives.

Example 19. The catalyst of example 2 experience in the Hydrotreating process of straight-run gasoline fraction 85-180oC containing 0,019 sulfur and 0,0003 nitrogen. Test conditions: a pressure of 3 MPa, the space velocity of the feed 6 h-1the ratio of hydrogen raw material 200 ml3/m3. The catalyst pre-sarnaut diesel fraction similar to example 1. When the test select a temperature sufficient to clean the substrate from sulfur to a residual content of 0.0001 Examples 19-20 illustrate the possibility of effective application of proposed method the prepared catalyst for Hydrotreating gasoline fractions.

Example 21. The Hydrotreating catalyst of example 2 is subjected to atmospheric gasoil, wikipedi within 280-380oC. the sulfur and nitrogen in atmospheric gasoil 1.5 and was 0.026, respectively. Test conditions: a pressure of 4 MPa, a temperature of 380oC, the volumetric feed rate 6 h-1the ratio of hydrogen raw material 300 nm3/m3. The sulfur content and will asobara vacuum gasoil, wikipedi within 320-523 oC and containing 1.9 and 0,052 sulfur and nitrogen, respectively. Test conditions: a pressure of 6 MPa, a temperature of 380oC, the volumetric feed rate 2 h-1the ratio of hydrogen raw 1000 nm3/m3. The content of sulfur and nitrogen in the hydrotreated product 0.068 and 0,031 respectively. Examples 21-22 illustrate the suitability of the proposed method of preparing a catalyst for Hydrotreating heavy oil fractions.

1. The preparation method of catalyst for Hydrotreating petroleum fractions, including separate precipitation of sodium aluminate acid at room temperature and the boiling, the subsequent mixing of modifications of aluminum hydroxide, hot and cold precipitation, washing the precipitate of aluminum hydroxide, the carrier impregnated with a solution of compounds of molybdenum and Nickel or cobalt, forming, drying and calcination of the catalyst, characterized in that the molding is subjected to the aluminum hydroxide and/or alumina powder in a mixture with 0.5 to 12% kaolin, dried and calcined received media and carry out its impregnation with a solution of compounds of these metals.

2. The method according to p. 1, characterized in that the mixture of modified aluminum hydroxide cold and grief is="ptx2">

3. The method according to p. 1, characterized in that the calcination of the catalyst is carried out at 220 420oC.

 

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