Method of regeneration of spent nickel-containing hydrogenation catalyst

 

(57) Abstract:

The invention relates to the field of inorganic chemistry, more specifically to methods of regeneration of spent catalyst in the hydrogenation of 1,4-butynediol in 1,4-butanediol. A method of regeneration of a copper-Nickel-chrome-on-kaolin catalyst by treating it 22-27 wt.% a solution of nitric acid followed by thermoremanence media when 360 - 400oC, impregnation with a solution of salts, having a composition, in terms of metal, g/DM3: Ni 170 - 180, Cu 43 - 46, Cr 12 - 13, by drying and calcining at 360 - 400oC.

The invention relates to the field of inorganic chemistry, more specifically to methods of regeneration of spent catalyst in the hydrogenation of 1,4-butynediol in 1,4-butanediol.

In the process of producing 1,4-butanediol by the method of catalytic reduction of 1,4-butandiol used copper-Nickel-chrome-on-granulated kaolin catalyst [1] the Process is carried out in a flow-through mode, skipping 12% solution of the original 1,4-butandiol in their own hydrogenation product. The pressure of the circulating hydrogen is 24.0 MPa, the temperature in the reaction zone 80 140oC, the volumetric feed rate of 0.2 h-1, volumetric feed rate of hydrogen on the catalyst 1600 cimel composition, wt. Cu 1,3 1,5; Ni 5,0 7,0; Cr 0,3 0,4; kaolin to 100.

The service life of the catalyst up to DN 100, after which the catalyst was unloaded and sent to the dump.

Known [2] the method of regeneration of the Nickel-copper-on-silica gel catalyst in the hydrogenation of 1,4-butynediol in 1,4-butanediol.

The catalyst composition, wt. NiO 8,6, CuO 8,4, SiO283,

with features:

bulk density, g/cm30,75

specific surface area, m2/g 250

porosity, 35

regenerate after 4 to 6 months by burning coke at 300oC with subsequent recovery. The service life of the catalyst 1 year.

The disadvantage of this method is the inability to use it for regeneration of the catalyst is copper-Nickel-chromium-on-kaolin, because at high temperature regeneration occurs sintering of the catalyst deposited on the surface of silica particles carried away from the stage akinrinola synthesis of 1,4-butandiol.

There is a method of regeneration of contaminated metals catalysts [3] used in the catalytic conversion of hydrocarbons, according to which the spent catalyst is washed with an aqueous solution of ammonium compounds, and then with a solution of rare earth elements. Modification CLASS="ptx2">

In the method [4] regeneration of the catalyst for catalytic cracking is carried out in several stages: heated 2 h in a stream of air at 732oC, then, after purging with nitrogen, sarnaut, giving 100% H2S within 4 hours After cooling in a stream of nitrogen to 343oC serves 100% chlorine for 1.5 hours Then served spicy water vapor to purge the catalyst or first cooled catalyst to room temperature, and then washed with water in an amount of 4 parts to 1 part catalyst.

The disadvantage of these methods is their unsuitability for recovery of the catalyst in the hydrogenation of 1,4-butynediol, because there is a complete deactivation of the catalyst components chlorine - and sulfur-containing components.

Known [5] the method of regeneration of spent catalyst in the hydrogenation of 1,4-butynediol 1,4-butanediol, according to which use Nickel-aluminum skeletal catalyst after the loss of activity is subjected to activation by rinsing it with distilled water, taken in an amount of 0.5 - 1.0 volume from the bulk volume of the regenerated catalyst supporting when washing the hydrogen pressure in the system up to 90% of the operating pressure of the hydrogenation process.

Most is-butanediol by processing the lost activity of the catalyst solutions of organic acids, for example, citric, succinic, or tartaric [6] the prototype. According to the prototype, the concentration of acid in the wash solution of 1.1 to 6.2% and the feed rate of the leaching solution 1500 l/min at 15000 kg loaded catalyst for 50 hours After regeneration of the catalyst solution of acid re-activation of the catalyst with a solution of NaOH during 6,7 hours and then carry out the hydrogenation process. The service life of the catalyst between regenerations to 583 hours May conduct up to 10 regenerations of the catalyst prior to final discharge.

The disadvantage of this method, including the method of the prototype is complete unsuitability for the regeneration of the Cu-Ni-Cr-on-kaolin catalyst, because the way is the prototype after the preliminary regeneration of the catalyst solutions of organic acids provide additional reactivation of the regenerated catalyst with a solution of sodium hydroxide. This technique is effective for alloy catalysts, because due to dissolution of the alkali portion of the aluminum in the original Ni-Al alloy is formed an additional amount of catalytically active Nickel.

When carrying out the regeneration of the catalyst Cu-Ni-Cr-on-kaolin in the method prototype there are no processes races is">

The purpose of the invention is the development of technology for the regeneration of copper-Nickel-chrome-on-kaolin catalyst hydrogenation of 1,4-butynediol 1,4-butanediol, to reduce the metal consumption, and media in the production of the catalyst.

To achieve this goal regeneration of spent Cu-Ni-Cr-on-kaolin catalyst is carried out by treatment of the catalyst with a solution of an inorganic acid, for example, nitrogen, at elevated temperatures, thermoremanence laundered media followed by impregnation with an aqueous solution of salts, drying and calcining.

In accordance with the proposed method, the process of regeneration of the spent catalyst is as follows.

The spent catalyst is treated with 22 27% nitric acid, taken in the ratio of catalyst acid 0,6 1 at 90oC for 4 h the resulting solution of metal salts in nitric acid recovered by evaporation to the density of a solution of 1.6 kg/DM3and adjust the composition of the resulting solution to routine additions of nitrate of Nickel and chromium trioxide, receiving the composition of the solution, g/DM3: Nickel 170 180; copper 43 - 46; chrome 12 13.

Media remaining after removal of metals AZ is the temperature. The cooled carrier impregnated with regenerated or fresh aqueous solution of salts, taken in the ratio of carrier solution 1 to 1.25 for 1.5 h at 60oC.

The impregnated carrier is dried and calcined in air flow at 360 - 400oC for 48 hours

Get ready to use the regenerated catalyst MNH-R with the following characteristics:

bulk density, kg/DM30,97 0,98

composition, wt.

Cu 1,3 1,5

Ni 5,0 7,0

Cr 0,3 0,5

kaolin to 100.

Regenerated the proposed method, the catalyst loaded into the reactor, creating a circulation of hydrogen at 1600 nm3/m3catalyst, a pressure of 240 MPa and activate the catalyst by heating it to a temperature of 170oC and maintaining at this temperature for 20 hours and Then the catalyst was cooled to a temperature of 60oC and start feeding raw materials 12% solution of 1,4-butandiol 1,4-butanediol at a rate of 0.2 h-1.

A distinctive feature of the proposed method is: use for the regeneration of spent catalyst nitric acid concentration of 22

27 wt. thermoremanence media calcining at 360 400oC; impregnating the regenerated nositeli at 360 400oC.

In the invention the conditions of the regeneration of the oxide copper-Nickel-chrome-on-kaolin catalysts using for preparation of a catalyst for the hydrogenation of 1,4-butynediol spent kaolin and salt solution, past the proposed procedure regeneration.

The obviousness of the proposed solution is that the exhaust kaolin media, after removal of the catalyst metal by means of nitric acid, in the proposed conditions of regeneration restores its characteristics, which allows to obtain a regenerated catalyst with the properties of the freshly prepared.

The invention is industrially applicable, because its implementation does not require any special equipment or inaccessible and expensive raw materials.

Example 1. The spent catalyst in the form of granules of size 3 to 7 mm in the amount of 1.2 kg is placed in a solution of 25% nitric acid taken in the quantity of 2 DM3and under stirring at a temperature of 90oC withstand 4 hours and Then the resulting salt solution is decanted, and the remaining kaolin media while stirring, washed with 30 min 1,2 DM3demineralized water.

The industry is SUP>C/h to a temperature of 380oC and kept at this temperature for 4 h, maintaining the speed of the air flow 350 bat3/h, then cooled in air flow to the 40oC speed 30oC/h and strain into a treatment tub in which is placed a 1.5 DM3the solution of metal nitrates with the following content, g/DM3in terms of metals: Ni 180, 45 Cu, Cr and 12.5. The solution temperature 60oC, the impregnation time of 1.5 hours Impregnated carrier is removed from solution, is loaded into progulochnuju furnace, heated in a stream of air at a speed of 30oC/h up to 380oC and kept at this temperature for 48 h, then cooled at a speed of 30oC/h to 40oC and unload.

The resulting catalyst has the following characteristics:

bulk density, kg/DM30,97

composition, wt. including

Nickel 6,38

Copper 1,38

Chrome 0,41

Kaolin Else

The catalyst in accordance with the requirements of the regulations are loaded into a tubular reactor at a rate of 1 DM3the system is blown from the air with hydrogen, then include the circulation of hydrogen at 1600 h-1and raise the pressure up to 24 MPa at a speed of 2.5 MPa/h When the preset pressure is heated catalyst with scorgie 12% solution of 1,4-butandiol 1,4-butanediol with a bulk velocity of 0.2 h-1.

The conversion of 1,4-butandiol for pass 100% selectivity of the formation of 1,4-butanediol 88 mol.

Example 2. The regeneration of spent catalyst carried out as described in example 1, except that the concentration of nitric acid 22 wt. and calcining the washed and impregnated carrier is carried out at 360oC.

When tested catalyst as in example 1, the conversion of 1,4-butandiol for the passage of 99.5% selectivity of the formation of 1,4-butanediol 85,8 mol.

Example 3. The regeneration of spent catalyst carried out as in example 1, except that the concentration of nitric acid 27 wt. and calcining the washed media and impregnated catalyst is carried out at 400oC.

During testing of the catalyst, the conversion of 1,4-butandiol equal to 100% selectivity of the reaction to 87.1 mol.

Example 4 for comparison. For testing hydrogenation process in the conditions of example 1 use the standard MNH catalyst composition: Ni 6,1; Cu 1,32; Cr 0,39; kaolin to 100.

During testing of the catalyst, the conversion of 1,4-butandiol equal to 100% selectivity of the reaction of 87.3 mol.

Method of regeneration of spent Nickel-containing hydrogenation catalyst, on the, trichosis the fact that the media after separation of the solution is dried and calcined at 360 400oSince then impregnated with an aqueous solution of salts containing (in terms of metal), g/DM3:

Nickel 170 180

Copper 43 46

Chrome 12 13

dried and calcined at 360 400oC.

 

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