# US 10,501,694 B2 · Selective hydrogenation process using a nickel catalyst prepared with an additive containing an amine or amide function or an amino acid

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- Number: US 10,501,694 B2
- Document ID: US10501694B2
- Status: Granted
- Kind: B2
- Application number: 15/852,337
- Filed: 2017-12-22
- Published: 2018-06-28
- Granted: 2019-12-10
- Earliest claimed: 2016-12-22
- Assignees: Ifp Energies Nouvelles
- Applicants: IFP Energies nouvelles
- Inventors: Anne-Claire Dubreuil; Agathe Martel
- Web page: https://patentgrep.com/patent/US10501694B2

## CPC

- C10G 45/36: containing nickel or cobalt metal, or compounds thereof
- B01J 23/755: Nickel
- B01J 31/0238: {with a primary amino group}
- B01J 31/0247: {Imides, amides or imidates (R-C=NR(OR))}
- B01J 31/04: containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)}
- B01J 35/393: {Metal or metal oxide crystallite size}
- B01J 35/613: {10-100 m2/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 35/77: Compounds characterised by their crystallite size
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- B01J 37/0205: {in several steps}
- B01J 37/0236: {Drying, e.g. preparing a suspension, adding a soluble salt and drying}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/084: {Decomposition of carbon-containing compounds into carbon}
- B01J 37/088: {Decomposition of a metal salt}
- C07C 7/163: by hydrogenation
- B01J 21/04: Alumina
- B01J 2231/645: of C=C or C-C triple bonds
- B01J 2235/00: Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts
- B01J 2531/847: Nickel
- 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
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

Selective hydrogenation of polyunsaturated compounds containing at least 2 carbon atoms per molecule contained in a hydrocarbon feed with a final boiling point of 300° C. or less, in the presence of a catalyst having a support formed from alumina and an active phase constituted by nickel, said catalyst being prepared by: i) bringing said support into contact with at least one solution containing at least one precursor of nickel; ii) bringing said support into contact with at least one solution containing at least one organic compound comprising at least one amine function with the empirical formula CxNyHz in which x is in the range 1 to 20, y=1−x and z=2−2x+2, or an amide function, or an amino acid, iii) drying said impregnated support at a temperature of less than 250° C.; steps i) and ii) being carried out separately, in any order, or simultaneously.

## Claims

### Claim 1

A process comprising selective hydrogenation of polyunsaturated compounds containing at least 2 carbon atoms per molecule, contained in a hydrocarbon feed that is a C2 cut from steam cracking, a C2-C3 cut from steam cracking, a C3 cut from steam cracking, a C4 cut from steam cracking, a C5 cut from steam cracking or gasolines from steam cracking, with a final boiling point of 300° C. or less, said process being carried out at a temperature in the range 0° C. to 300° C., at a pressure in the range 0.1 to 10 MPa, in liquid phase at a molar ratio of hydrogen/(polyunsaturated compounds to be hydrogenated) in the range 0.1 to 10 and at an hourly space velocity in the range 0.1 to 200 h−1, or in gas phase at a molar ratio of hydrogen/(polyunsaturated compounds to be hydrogenated) in the range 0.5 to 1000 and at an hourly space velocity in the range 100 to 40000 h−1, in the presence of a catalyst comprising a support formed from alumina and an active phase constituted by nickel, said catalyst being prepared by a process comprising at least:
i) bringing said support into contact with at least one solution containing at least one precursor of nickel;
ii) bringing said support into contact with at least one solution containing at least one organic compound having 1 to 20 carbon atoms and at least one amine function with the empirical formula CxNyHz in which 1≤x≤20, 1≤y≤x, 2≤z≤2x+2, or at least one amide function, or at least one amino acid, to produce an impregnated support,
iii) drying said impregnated support at a temperature of less than 250° C. so as to obtain a dried catalyst comprising nickel in the form of nanoparticles measured, in oxide form, of 1.5 to 10.0 nm;
i) and ii) being carried out separately, in any order, or simultaneously.

### Claim 2 (depends on 1)

The process as claimed in claim 1, further comprising at iv) at least one calcination of said dried catalyst obtained in iii) at a temperature in the range 250° C. to 1000° C.

### Claim 3 (depends on 1)

The process as claimed in claim 1, wherein i) and ii) are carried out simultaneously.

### Claim 4 (depends on 1)

The process as claimed in claim 1, wherein i) is carried out before ii).

### Claim 5 (depends on 1)

The process as claimed in claim 1, wherein ii) is carried out before i).

### Claim 6 (depends on 1)

The process as claimed in claim 1, wherein i) and/or ii) is (are) carried out by dry impregnation.

### Claim 7 (depends on 1)

The process as claimed in claim 1, wherein the catalyst has a nickel content is in the range 1% to 35% by weight with respect to the total catalyst weight.

### Claim 8 (depends on 1)

The process as claimed in claim 1, wherein the at least one organic compound is an amino acid.

### Claim 9 (depends on 1)

The process as claimed in claim 1, wherein the at least one organic compound comprises at least one amide function that is an acyclic amide function or a cyclic amide function.

### Claim 10 (depends on 1)

The process as claimed in claim 1, wherein the at least one organic compound comprises at least one amide function and at least one other function which differs from the at least one amide function, that is a carboxylic acid function or an alcohol function.

### Claim 11 (depends on 9)

The process as claimed in claim 9, wherein the at least one organic compound furthermore comprises a supplemental nitrogen heteroatom and is urea, N-methylurea, N,N′-dimethylurea, 1,1-dimethylurea or tetramethylurea, in any one of their isomeric forms.

### Claim 12 (depends on 1)

The process as claimed in claim 1, wherein the feed is a C2 cut from steam cracking or a C2-C3 cut from steam cracking, and in which process in a gas phase the molar ratio of (hydrogen)/(polyunsaturated compounds to be hydrogenated) is in the range 0.5 to 1000, the temperature is in the range 0° C. to 300° C., the hourly space velocity (HSV) is in the range 100 to 40000 h−1, and the pressure is in the range 0.1 to 6.0 MPa.

### Claim 13 (depends on 1)

The process as claimed in claim 1, wherein the feed is gasolines from steam cracking and in which process in a liquid phase the molar ratio of (hydrogen)/(polyunsaturated compounds to be hydrogenated) is in the range 0.5 to 10, the temperature is in the range 0° C. to 200° C., the hourly space velocity (HSV) is in the range 0.5 to 100 h−1, and the pressure is in the range 0.3 to 8.0 MPa.

### Claim 14 (depends on 1)

The process as claimed in claim 1, wherein the polyunsaturated compounds containing at least 2 carbon atoms per molecule are diolefins, acetylenes and/or alkenylaromatics.

### Claim 15 (depends on 1)

The process as claimed in claim 1, carried out in gas phase.

### Claim 16 (depends on 1)

The process as claimed in claim 1, carried out in liquid phase.