Method of regenerating exhausted oil feedstock hydrofining catalyst

FIELD: petrochemical process catalysts.

SUBSTANCE: invention, in particular, relates to catalysts based on nickel, cobalt, molybdenum, aluminum oxides. Regeneration of exhausted catalyst is carried out through heat treatment in air atmosphere at 550-600°C for 1-1.5 h followed by: mechanical activation at energy concentration at least 6.6 W/g on vibrational mill; grinding into powder; adding at stirring a mixture containing nitric acid solution (concentration 3,5-7%), cobalt or nickel nitrate and ammonium paramolybdate; molding; drying; and calcination.

EFFECT: simplified regeneration procedure and enabled restoration of catalyst strength.

1 tbl, 12 ex

 

The invention relates to the refining, petrochemical and production of ammonia, methanol and hydrogen, in particular to a method of regenerating exhausted aluminoborosilicate and alumonickelsilicate catalysts for Hydrotreating processes of crude oil, natural and process gas.

There is a method of regeneration of catalysts based on oxides of Nickel, cobalt, molybdenum, aluminum, silicon for Hydrotreating of crude oil by grinding the spent catalyst in powder processing 10-20% solution of nitric acid, shaping, provolkoi within 24 hours, drying at 120-150°C for 6-12 hours, calcining at 500-550°C for 6-12 hours with subsequent manual processing of the obtained granules with solutions of salts of ammonium molybdate and cobalt nitrate or Nickel, with intermediate drying and calcining at 500-550°C for 6-12 hours (SU 738660, B 01 J 23/94, 1980).

The disadvantage of this method is a multistage energy-intensive technology, which leads to high cost of regeneration of the catalyst.

The closest in technical essence and the achieved result is a method for the regeneration of spent catalysts for Hydrotreating of crude oil on the basis of the oxides of Nickel, cobalt, molybdenum, aluminum, silicon, comprising the grinding of the catalyst powder, etc is stirring contribute nitrate salt of cobalt or Nickel, the resulting mixture is treated with 10-20% nitric acid, then it make salt molibdenovokislogo ammonium, followed by molding, the crop has wilted, dried at 120-160°C, annealing at 500-550°With (SU 825136, B 01 J 23/94, 1981).

The disadvantage of this method is the complicated technology of application of active ingredients with a large number of concentrated nitric acid, which leads to the release of significant quantities of nitrogen oxides during calcination, the presence of stage of wilting reduces the performance of the hardware.

The task of the invention is the recovery of the activity and durability of spent catalysts based on oxides of Nickel, cobalt, molybdenum and aluminum, used for Hydrotreating of crude oil, the simplification of the process of regeneration.

This object is achieved in that the spent catalyst in the Hydrotreating of crude oil is subjected to heat treatment in a furnace in air atmosphere at a temperature of 550-600°C for 1-1 .5 hours, and then the granules are subjected to mechanical activation with energonapryazhennosti not less than 6.6 W/g by grinding in a vibrating mill to a fineness of grind of more than 100 μm 10-20%, in the milled catalyst before forming when mixing the injected mixture containing 3,5-7% concentration solution of nitric acid and nitrate salts of cobalt alinikula and paramolybdate ammonium further catalyst mass is formed, dried and calcined.

The essence of the proposed method of regeneration as compared with the known is the following: the heat treatment of the granules completely or partially spent catalyst at a temperature of 550-600°allows you to remove unwanted impurities in the form of deposits of carbon and organic compounds, which leads to increased activity, allows for mechanical activation of the regenerated catalyst in the mills vibrating type, characterized by shock-abrasive action; mechanical activation (method for directional control of physico-chemical properties of solids and the creation of defective structures under the action of the applied mechanical energy) at the stage of grinding pellets reduces the concentration of nitric acid, to avoid a stage of wilting, to obtain a catalyst with high activity and strength; the introduction of the regenerated catalyst mixture of nitric acid and nitrate salts of cobalt or Nickel and paramolybdate ammonium can increase the activity of the catalyst due to the formation of new active sites.

This method allows you to fully restore the activity and durability of spent catalysts based on oxides of cobalt, Nickel, molybdenum and aluminum, used for Hydrotreating of crude oil, as well as to simplify the process regenerat is I.

The proposed method is as follows.

The spent catalyst based on oxides of Nickel, cobalt, molybdenum and aluminum is subjected to heat treatment in an atmosphere of air at a temperature of 550-600°C for 1-1 .5 hours, then loaded into the vibrating mill and produce grinding with energonapryazhennosti (specific consumption of energy input) is not less than 6.6 W/g to fineness of grinding more than 100 microns 10-20%. The resulting powder was loaded into the mixer and treated under stirring for 0.5-1 hour the mixture containing 3,5-7%concentration of nitric acid, nitrate of cobalt or Nickel and paramolybdate ammonium. The resulting mass is molded, dried at a temperature of 100-110°C for 0.5-1 hour and calcined at a temperature of 450-500°within 2 hours.

Example 1. 150 kg of waste, lost its industrial activity of the catalyst chemical composition, wt.% Soo - 3,8; NGO3or 11.3; - 4,6; Al2O3- the rest is subjected to heat treatment in an atmosphere of air at a temperature of 550°C for 1.5 hours, loaded in a vibrating mill and produce grinding (mechanical activation) energonapryazhennosti 9.5 watts/g to fineness of grinding faction more than 100 μm 10%.

Then 130 kg of powder loaded into the mixer and treated with a mixture containing 60 liters of 3.5% solution of nitric acid, 1,66 kg paramolybdate ammonium and 2.6 kg of nitrogen the number of cobalt for 0.5 hours.

The resulting mass with humidity 28% molded, dried in a dryer at a temperature of 100-110°C for 0.5-1 hour and calcined at a temperature of 500°within 2 hours.

The finished catalyst chem. composition, wt.%:

Soo 4,3

Moo312,3

With 0,04

Al2O3the rest

The ratio of mechanical strength 1,95 kg/mm

Example 2. 150 kg of waste lost its industrial activity Al-Co-Mo catalyst in the chemical composition of example 1 is subjected to heat treatment in air at 600°C for 1 hour and grind in the conditions of example 1 to fineness of grinding more than 100 microns 20%.

Then 130 kg of powder loaded into the mixer and treated with a mixture containing 60 liters of 3.5% solution of nitric acid, 4,98 kg paramolybdate ammonium and 5.2 kg of cobalt nitrate for 0.5 hours. Further processing is carried out in the conditions of example 1.

The calcination is carried out in a furnace at a temperature of 450°C for 2 hours. The finished catalyst chem. composition, wt.%:

Soo 4,8

Moo314,3

From 0.02

Al2About3the rest

The ratio of mechanical strength of 2.2 kg/mm

Primer kg of waste lost its industrial activity Al-Co-Mo catalyst in the chemical composition of example 1 is subjected to heat treatment under the conditions of example 1 and milled with energonapryazhennosti 6.6w/g in a vibrating mill to fineness SIP the La fraction more than 100 μm 10%.

Then 130 kg of powder loaded into the mixer and treated with a mixture of 60 liters of 7% concentration of nitric acid solution, 4,98 kg paramolybdate ammonium and 5.2 kg of cobalt nitrate. Further processing is carried out in the conditions of example 1.

The finished catalyst chem. composition, wt.%:

Soo 4,8

Moo314,3

With 0,04

Al2O3the rest

The ratio of mechanical strength of 2.35 kg/mm

Example 4. 150 kg of waste lost its industrial activity Al-Co-Mo catalyst in the chemical composition of example 1 is subjected to heat treatment in an atmosphere of air at a temperature of 600°C for 1 hour and grind in the conditions of example 1 to fineness of grinding faction more than 100 μm to 15%.

Then 130 kg of powder loaded into the mixer and treated with a mixture containing 60 liters of 7% concentration of nitric acid solution, 1,66 kg paramolybdate ammonium and 2.6 kg of cobalt nitrate. Further processing is carried out in the conditions of example 1.

The calcination is carried out in the furnace CPS at a temperature of 450°within 2 hours.

The finished catalyst chem. composition, wt.%:

Soo 4,3

Moo312,3

With 0,04

Al2About3the rest

The ratio of mechanical strength of 2.3 kg/mm

Example 5. 150 kg of waste lost its industrial activity Al-Ni-Mo catalyst chemical composition, wt.%: NiO - 4,1; NGO3to 12.0; P - 2,1; Al2 About3- the rest is subjected to heat treatment in an atmosphere of air at a temperature of 550°C for 1.5 hours and grinding with energonapryazhennosti 6.6w/g in a vibrating mill to a fineness of grind faction more than 100 microns 20%.

Then 130 kg of powder loaded into the mixer and treated with a mixture containing 60 liters of 3.5% concentration of nitric acid solution, 4,98 kg paramolybdate ammonium and 5.2 kg of Nickel nitrate. Further processing is carried out in the conditions of example 1. The calcination is carried out in a furnace at a temperature of 500°within 2 hours.

The finished catalyst chem. composition, wt.%:

NiO 5,1

Moo313,5

Al2About3the rest

The ratio of mechanical strength of 2.3 kg/mm

Example 6. 150 kg of waste, lost its industrial activity of the catalyst of the chemical composition of the example 5 is subjected to heat treatment in an atmosphere of air at a temperature of 600°C for 1 hour and grind with energonapryazhennosti 8.5 W/g in a vibrating mill to a fineness of grind faction more than 100 μm 10%.

Then 130 kg of powder loaded into the mixer and treated with a mixture consisting of 60 liters of 7% concentration of nitric acid solution, 1,66 kg paramolybdate ammonium and 2.6 kg of Nickel nitrate. Further processing is carried out in the conditions of example 1. The calcination is carried out in a furnace at a temperature of 450°within 2 hours.

The finished catalyst is them. composition, wt.%:

NiO 4,6

Moo313,0

With 0,04

Al2O3the rest

The ratio of mechanical strength of 2.15 kg/mm

Example 7 (comparative). 150 kg of waste lost its industrial activity Al-Co-Mo catalyst in the chemical composition of example 1 without preliminary heat treatment is subjected to grinding and further processing in the conditions of example 1.

The finished catalyst chem. composition, wt.%:

Soo 4,3

Moo312,3

With 0,04

Al2O3the rest

The ratio of mechanical strength of 1.9 kg/mm

Example 8 (comparative). 150 kg of waste, lost its industrial activity Al-Ni-Mo catalyst chemical composition in example 5 without preliminary heat treatment is subjected to grinding and further processing in the conditions of example 1. The finished catalyst chem. composition, wt.%:

NiO 4,6

Moo313,0

Al2O3the rest

The ratio of mechanical strength of 1.55 kg/mm

Example 9 (comparative). 150 kg of waste, lost its industrial activity Al-Co-Mo catalyst in the chemical composition of example 1 is subjected to grinding with energonapryazhennosti of 2.9 W/g on a ball mill to a fineness of grind of less than 150 μm and further processing in the conditions of example 1.

The finished catalyst chem. composition, wt.%:

Soo 4,3

Moo312,3

With 0,04

Al2O 3the rest

The ratio of mechanical strength of 1.05 kg/mm

Example 10 (comparative). 130 kg of waste industrial Al-Ni-Mo catalyst following chemical composition, wt.%:

NiO 4,1

Moo312,6

Al2About3the rest

Subjected to grinding with energonapryazhennosti of 2.9 W/g on a ball mill to a fineness of grind of less than 150 μm and further processing in the conditions of example 5. The finished catalyst chem. composition, wt.%:

NiO 4,8

Moo314,5

Al2O3the rest

The ratio of mechanical strength of 1.8 kg/mm

Example 11 (prototype). 130 kg of waste, lost its industrial activity Al-Co-Mo catalyst following him. composition, wt.%:

Soo 3,8

Moo313,0

Al2O3the rest

grind into powder to fineness of grind of less than 150 μm. Then, 100 kg of the obtained powder is loaded into the mixer and add 4.3 kg of salt is cobalt nitrate, stirred for 15 min and treated with 90 l of 20%concentration of nitric acid, the mass is stirred for 15 min and add 1,88 kg salt paramolybdate ammonium stirred at 85-98°30 minutes the resulting mass is formed into pellets that provalivajut 12 hours, dried for 2 hours at 120°and calcined for 6 h at 500°C. the Finished catalyst chem. composition, wt.%:

Soo 4,8

Moo314,5

Al2O3the rest

The coefficient m is the mechanical strength of 2.25 kg/mm

Example 12 (prototype). 130 kg of waste, lost its industrial activity Al-Ni-Mo catalyst chem. composition, wt.%:

NiO 4,1

Moo312,6

Al2O3the rest

grind into powder to fineness of grinding particles less than 150 microns. Then, 100 kg of the obtained powder is loaded into the mixer, add 14,6 kg nitrate salt of Nickel, stirred for 15 min and treated with 90 l of 20%concentration nitric acid, stirred for 20 min, add 9,0 kg paramolybdate ammonium stirred while heated to 90-100°30 min, molded, provalivajut 12 hours at 120°C, calcined 6 hours at 500°C. the Regenerated catalyst has a chemical composition, wt.%:

NiO 7,2

Moo318,5

Al2About3the rest

The ratio of mechanical strength of 1.85 kg/mm

The activity of the catalysts was determined by the following method.

In accordance with THE 113-03-00209510-86-2001 on allocability the catalyst and THE 113-03-00209510-96-2003 on aluminumalloy catalyst technique consists in the withdrawal of the operating mode (360°C)preliminary asemanii catalyst for 2 hours (to stabilize the hydrogenating capacity), reducing the temperature to 270°With a determination of the degree of hydrogenation. Test conditions: space velocity of 10,000 h-1the concentration of diethylsulfide in terms of CE is at 16000 mg/m 3.

Comparative results of tests of the catalysts regenerated by the proposed method on the prototype and fresh industrial catalysts chemical composition, wt.%: Soo (NiO) To 3.8 Moo3- 11,6, Al2About3- rest in the Hydrotreating process is shown in the table.

1,4
The catalyst according to example No.Mechanical strength, kg/mm diameter granulesActivity according to the method %
11,9594
22,298
32,3595
42,395
52,398
62,1595
7 (comparative)1,985
8 (comparative)1,5594
9 (comparative)1,0580
10 (comparative)1,882
11 (prototype)2,2594
12 (prototype)1,8594
Fresh industrial Al-Co-Mo1,487
Fresh industrial Al-Ni-Mo87

From the table it is seen that the preliminary heat treatment in an atmosphere of air exhaust and lost its activity of catalysts based on oxides of cobalt, Nickel, molybdenum and aluminum and their mechanical activation with energonapryazhennosti not less than 6.6 W/g in a vibrating mill was possible to obtain catalysts with almost equal activity, and in some cases earlier in the process hydroservice with fresh industrial catalysts.

The use of mechanical activation with energonapryazhennosti not less than 6.6 W/g in a vibrating mill allowed to obtain mechanically strong catalyst, the ratio of the strength of all samples is at the level of 1.95 to 2.35 kg/mm, which exceeds the strength factor of industrial catalysts, in comparison with the prototype, the mechanical strength of the samples on the examples above, or practically at the same level.

Use for the regeneration of spent catalysts proposed method improves performance by eliminating the stage of wilting in comparison with the known method and simplifies the process of regeneration.

Method of regenerating spent catalyst for Hydrotreating of crude oil on the basis of oxides of Nickel or cobalt, oxides of molybdenum and aluminum, including refining catalyst is in the powder, the introduction of nitric acid, the introduction of active components - nitrate salts of cobalt or Nickel and paramolybdate ammonium, forming, drying, calcining, wherein the spent catalyst before grinding is subjected to heat treatment in an atmosphere of air at a temperature of 550-600°C for 1-1 .5 h, and then the granules are subjected to mechanical activation with energonapryazhennosti not less than 6.6 W/g in a vibrating mill to a fineness of grind faction more than 100 microns 10-20%, in the milled catalyst before forming under stirring injected a mixture of 3,5-7% concentration solution of nitric acid and nitrate salts of cobalt or Nickel and paramolybdate ammonium.



 

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