# US 10,307,738 B2 · Nickel-based mesoporous catalyst and use thereof in hydrogenation

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- Number: US 10,307,738 B2
- Document ID: US10307738B2
- Status: Granted
- Kind: B2
- Application number: 15/509,873
- Filed: 2015-08-21
- Published: 2017-09-14
- Granted: 2019-06-04
- Earliest claimed: 2014-09-11
- Assignees: Ifp Energies Nouvelles
- Applicants: IFP Energies Nouvelles
- Inventors: Malika Boualleg; Anne-Claire Dubreuil; Emily Maille; Cecile Thomazeau
- Web page: https://patentgrep.com/patent/US10307738B2

## CPC

- B01J 23/755: Nickel
- B01J 21/04: Alumina
- B01J 35/19: {Catalysts containing parts with different compositions}
- B01J 35/393: {Metal or metal oxide crystallite size}
- B01J 35/45: Nanoparticles
- B01J 35/50: characterised by their shape or configuration
- B01J 35/60: characterised by their surface properties or porosity
- B01J 35/615: {100-500 m2/g}
- B01J 35/633: {less than 0.5 ml/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 35/647: {2-50 nm}
- B01J 35/66: Pore distribution
- B01J 37/0009: {Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst}
- B01J 37/009: {Preparation by separation, e.g. by filtration, decantation, screening}
- B01J 37/0201: {Impregnation}
- B01J 37/0205: {in several steps}
- B01J 37/0207: {Pretreatment of the support}
- B01J 37/0213: {Preparation of the impregnating solution}
- B01J 37/0236: {Drying, e.g. preparing a suspension, adding a soluble salt and drying}
- B01J 37/031: {Precipitation}
- B01J 37/035: {Precipitation on carriers}
- B01J 37/036: {to form a gel or a cogel}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/16: Reducing
- C01F 7/141: from aqueous aluminate solutions by neutralisation with an acidic agent
- C01F 7/34: Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
- C01F 7/441: by calcination
- C07C 7/163: by hydrogenation
- C10G 45/36: containing nickel or cobalt metal, or compounds thereof
- C10G 45/48: containing nickel or cobalt metal, or compounds thereof
- B01J 23/835: with germanium, tin or lead
- B01J 23/892: {Nickel and noble metals}
- B01J 37/18: with gases containing free hydrogen
- B01J 2235/00: Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- C01P 2006/12: Surface area
- C01P 2006/14: Pore volume
- C01P 2006/16: Pore diameter
- C10G 2300/705: Passivation
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01F: COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts of peroxyacids C01B15/00; sulfides or polysulfides of magnesium, calcium, strontium, or barium C01B17/42; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds other than ammonia or cyanogen containing nitrogen and non-metals and optionally metals C01B21/082; amides or imides of silicon C01B21/087}; metal {imides or} amides C01B21/092, {C01B21/0923}; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanic acid C01C3/14; salts of cyanamide C01C3/16; thiocyanates C01C3/20; {double sulfates of magnesium with sodium or potassium C01D5/12; with other alkali metals C01D15/00, C01D17/00})
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

A supported catalyst having a calcined, predominantly aluminum, oxide support and an active phase of 5 to 65% by weight nickel with respect to the total mass of the catalyst, said active phase having no group VIB metal, the nickel particles having a diameter less than or equal to 20 nm, said catalyst having a mesopore median diameter greater than or equal to 14 nm, a mesopore volume measured by mercury porosimetry greater than or equal to 0.45 mL/g, a total pore volume measured by mercury porosimetry greater than or equal to 0.45 mL/g, a macropore volume less than 5% of the total pore volume, said catalyst being in the form of grains having an average diameter comprised between 0.5 and 10 mm. The invention also relates to the process for the preparation of said catalyst and the use thereof in a hydrogenation process.

## Claims

### Claim 1

A supported catalyst comprising a calcined, predominantly aluminium, oxide support and an active phase comprising nickel, the nickel content being 5 to 65% by weight of said element with respect to the total mass of the catalyst, said active phase comprising no group VIB metal, the nickel particles having a diameter less than or equal to 20 nm, said catalyst having a mesopore median diameter greater than or equal to 14 nm, a mesopore volume measured by mercury porosimetry greater than or equal to 0.45 mL/g, a total pore volume measured by mercury porosimetry greater than or equal to 0.45 mL/g, a macropore volume less than 3.5% of the total pore volume, said catalyst being in the form of grains having an average diameter comprised between 0.5 and 10 mm.

### Claim 2 (depends on 1)

The catalyst according to claim 1, in which the mesopore median diameter of the catalyst is comprised between 18 and 25 nm.

### Claim 3 (depends on 1)

The catalyst Catalysts according to claim 1, in which the mesopore volume of the catalyst is 0.55 ml/g to 0.95 ml/g.

### Claim 4 (depends on 1)

The catalyst according to claim 1, in which the nickel content is 10 to 34% by weight of said element with respect to the total mass of the catalyst.

### Claim 5 (depends on 1)

The catalyst according to claim 1, containing no pores with a diameter between 2 and 7 nm.

### Claim 6 (depends on 1)

The catalyst according to claim 1, containing no micropores.

### Claim 7 (depends on 1)

A process for the preparation of a catalyst according to claim 1 comprising:
a) precipitating, in an aqueous reaction medium, at least one basic precursor that is sodium aluminate, potassium aluminate, ammonium hydroxide, sodium hydroxide or potassium hydroxide and at least one acidic precursor that is aluminium sulphate, aluminium chloride, aluminium nitrate, sulphuric acid, hydrochloric acid or nitric acid, in which at least one of the basic or acidic precursors comprises aluminium, the relative flow rate of the acidic and basic precursors is selected so as to obtain a pH of the reaction medium of 8.5 to 10.5 and the flow rate of the acidic and basic precursor(s) containing aluminium is adjusted so as to obtain a degree of progression in (a) of 5 to 13%, the degree of progression being defined as the proportion of alumina formed in Al2O3 equivalent during said precipitation in (a) with respect to the total quantity of alumina formed in Al2O3 equivalent at the end of (c) of the preparation process, said precipitation (a) taking place at a temperature of 20 to 90° C. and for a duration of 2 to 30 minutes;
b) heating the suspension obtained in (a) at a temperature of 40 to 90° C. for a duration of 7 to 45 minutes in order to obtain an alumina gel,
c) a second precipitation of the suspension obtained at the end of heating b) by adding, to the suspension, at least one basic precursor that is sodium aluminate, potassium aluminate, ammonium hydroxide, sodium hydroxide or potassium hydroxide and at least one acidic precursor that is aluminium sulphate, aluminium chloride, aluminium nitrate, sulphuric acid, hydrochloric acid or nitric acid, in which at least one of the basic or acidic precursors comprises aluminium, the relative flow rate of the acidic and basic precursors is selected so as to obtain a pH of the reaction medium of 8.5 to 10.5 and the flow rate of the acidic and basic precursor(s) containing aluminium is adjusted so as to obtain a degree of progression of the second precipitation of 87 to 95%, the degree of progression being defined as the proportion of alumina formed in Al2O3 equivalent during said second precipitation with respect to the total quantity of alumina formed in Al2O3 equivalent at the end of c) of the preparation process, said precipitation taking place at a temperature of 40 to 90° C. and for a duration of 2 to 50 minutes;
d) filtration of a suspension obtained at the end of the second precipitation c) in order to obtain an alumina gel,
e) drying said alumina gel obtained in d) in order to obtain a powder,
f) forming the powder obtained at the end of e) in order to obtain a crude material,
g) heat treating the crude material obtained at the end of f) at a temperature of 500 to 1000° C., in the presence or absence of an air flow containing up to 60% by volume of water, in order to obtain a calcined aluminium oxide support;
h) impregnating said support with a solution comprising the salt(s) of the precursor(s) of the nickel-based active phase;
i) drying said impregnated support at a temperature of 15 to 250° C. so as to obtain a dried catalyst,
j) optionally heat treating said dried catalyst at a temperature of 250 to 1000° C., in the presence or absence of water.

### Claim 8 (depends on 7)

The process according to claim 7, in which at least one reducing treatment k) is carried out in the presence of a reducing gas after i) or j) so as to obtain a catalyst comprising nickel at least partially in metallic form.

### Claim 9 (depends on 8)

The process according to claim 8, in which passivation l) is carried out with a sulphur- or oxygen-containing compound, or with CO2 before or after reducing treatment k).

### Claim 10 (depends on 7)

The process according to claim 7, in which the degree of progression of the first precipitation a) is 6 to 12%.

### Claim 11 (depends on 7)

The process according to claim 7, in which the acidic precursor of a) and c) is aluminium sulphate, aluminium chloride or aluminium nitrate, and in which the basic precursor of a) and c) is sodium aluminate or potassium aluminate.

### Claim 12 (depends on 1)

A hydrogenation process comprising contacting the catalyst according to claim 1, in the presence of hydrogen, with a feedstock of hydrocarbons containing polyunsaturated and/or aromatic compounds so as to obtain an at least partially hydrogenated effluent.

### Claim 13 (depends on 12)

The hydrogenation process according to claim 12 comprising selective hydrogenation of a hydrocarbon feedstock containing polyunsaturated compounds containing at least 2 carbon atoms per molecule and having a final boiling point less than or equal to 250° C. at a temperature of 0 to 500° C., at a pressure 0.1 to 20 MPa, at a hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio of 0.1 to 10 at an hourly space velocity HSV of 0.1 to 200 h−1 for a liquid feedstock, 100 to 15,000 h−1 for a gaseous feedstock.

### Claim 14 (depends on 12)

The hydrogenation process according to claim 12 in which a hydrogenation of the aromatics is carried out at a temperature of 30 to 350° C., at a pressure of 0.1 to 20 MPa, at a hydrogen/(aromatic compounds to be hydrogenated) molar ratio between 0.1 and 10 and at an hourly space velocity HSV of 0.05 to 50 h−1, said hydrocarbon feedstock containing aromatic compounds and having a final boiling point less than or equal to 650° C.