US 11,674,094 B2
Co-mixed catalyst produced from solutions containing heteropolyanions, method for the production thereof, and use of same in hydroconversion of heavy hydrocarbon feedstock
Thibault Corre, Rueil-Malmaison (FR); and Mathieu Digne, Rueil-Malmaison (FR)
Assigned to IFP Energies Nouvelles, Rueil-Malmaison (FR)
Appl. No. 17/262,530
Filed by IFP Energies nouvelles, Rueil-Malmaison (FR)
PCT Filed Jul. 18, 2019, PCT No. PCT/EP2019/069367
§ 371(c)(1), (2) Date Jan. 22, 2021,
PCT Pub. No. WO2020/020740, PCT Pub. Date Jan. 30, 2020.
Claims priority of application No. 1856810 (FR), filed on Jul. 23, 2018.
Prior Publication US 2021/0292662 A1, Sep. 23, 2021
Int. Cl. C10G 65/12 (2006.01); B01J 23/883 (2006.01); B01J 35/10 (2006.01); B01J 21/04 (2006.01); B01J 37/00 (2006.01); B01J 37/02 (2006.01); B01J 37/04 (2006.01); B01J 37/06 (2006.01); B01J 37/08 (2006.01); C10G 45/08 (2006.01); C10G 47/04 (2006.01)
CPC C10G 65/12 (2013.01) [B01J 21/04 (2013.01); B01J 23/883 (2013.01); B01J 35/109 (2013.01); B01J 35/1019 (2013.01); B01J 35/1042 (2013.01); B01J 35/1066 (2013.01); B01J 35/1076 (2013.01); B01J 37/009 (2013.01); B01J 37/0063 (2013.01); B01J 37/0213 (2013.01); B01J 37/04 (2013.01); B01J 37/06 (2013.01); B01J 37/082 (2013.01); C10G 45/08 (2013.01); C10G 47/04 (2013.01); C10G 2300/202 (2013.01); C10G 2300/205 (2013.01); C10G 2300/206 (2013.01)] 16 Claims
 
1. A process for preparing a catalyst comprising an active phase comprising molybdenum and nickel and/or cobalt, and an oxide matrix containing alumina, said catalyst comprising a total pore volume of at least 0.6 ml/g, a macropore volume of between 10.0% and 40.0% of the total pore volume, a mesopore volume of at least 0.5 ml/g and a mean mesopore diameter of greater than 5.0 nm, comprising the following stages:
a) a stage of preparing an aqueous solution of aluminum precursors comprising a first acidic precursor, chosen from aluminum sulfate, aluminum chloride, aluminum nitrate and their mixtures, and a first basic precursor, chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide, potassium hydroxide and their mixtures;
b) a stage of bringing the solution obtained on conclusion of stage a) into contact with a second basic precursor, chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide, potassium hydroxide and their mixtures, and with a second acidic precursor chosen from aluminum sulfate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid, nitric acid and their mixtures, in order to obtain a suspension, with at least one of the second basic or acidic precursors comprising aluminum, wherein a relative flow rate of the second acidic and basic precursors being chosen so as to obtain a pH of the suspension of between 7.0 and 10.0 and the flow rate of the second acidic and/or basic precursor(s), which contain aluminum, being adjusted so as to obtain a concentration as alumina equivalent in the suspension of between 10.0 and 80.0 g/l, at a temperature of between 20.0 and 90.0° C. and over a time of between 1 and 75 minutes;
c) filtering and washing the suspension obtained in stage b) in order to obtain a boehmite cake;
d) preparing a clear aqueous solution at a pH of between 3.5 and 8.0, comprising a salt of heteropolyanion of Keggin and/or lacunary Keggin and/or substituted lacunary Keggin and/or Anderson and/or Strandberg type or their mixtures, said salt exhibiting, in its structure, molybdenum and cobalt and/or nickel;
e) co-kneading the boehmite cake obtained on conclusion of stage c) with the clear aqueous solution obtained on conclusion of stage d) in order to form a paste;
f) shaping the paste obtained on conclusion of stage e) in order to form grains of catalyst precursor;
g) drying the grains obtained on conclusion of stage f), at a temperature of less than 250.0° C., in order to obtain dried grains of catalyst precursor; and
h) calcining the dried grains obtained on conclusion of stage g), at a temperature of between 250.0 and 1000.0° C.