# US 7,612,245 B2 · Method for selective hydrogenation of polyunsaturated compounds into monounsaturated compounds using a homogeneous catalyst

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- Number: US 7,612,245 B2
- Document ID: US7612245B2
- Status: Granted
- Kind: B2
- Application number: 10/519,355
- Filed: 2003-06-16
- Published: 2006-06-15
- Granted: 2009-11-03
- Earliest claimed: 2002-06-28
- Assignees: Institut Francais du Petrole
- Inventors: Gerard Hillion; Laurent Savary; David Proriol; Christophe Gautreau; Denis Uzio; Helene Olivier-Bourbigou
- Web page: https://patentgrep.com/patent/US7612245B2

## CPC

- B01J 35/60: characterised by their surface properties or porosity
- C10G 45/34: characterised by the catalyst used
- C10G 45/36: containing nickel or cobalt metal, or compounds thereof
- C10G 45/40: containing platinum group metals or compounds thereof
- B01J 31/0234: {Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds}
- B01J 31/18: containing nitrogen, phosphorus, arsenic or antimony {as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms (double metal cyanides B01J27/26; N-heterocyclic carbenes B01J31/2265)}
- B01J 31/2204: {the ligands containing oxygen or sulfur as complexing atoms}
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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

## Abstract

A process for the selective hydrogenation of diolefinic compounds to mono-olefinic compounds uses a catalyst composition comprising at least one salt of a transition metal from groups IB, IIB, VB, VIB, VIIB and VIII of the periodic table, at least one ligand and at least one organometallic reducing agent, optionally in the presence of a non-aqueous ionic liquid selected from the group formed by liquid salts with general formula Q+A− (in which Q+ represents a quaternary ammonium and/or quaternary phosphonium and A− represents any anion which can form a liquid salt below 90° C.).

## Claims

### Claim 1

A process for the selective hydrogenation of 1,3-butadiene contained in a feed, comprising the passage of a feed containing 1,3-butadiene in contact with a liquid catalyst composition, characterized in that said liquid catalyst composition comprises at least one salt of a transition metal from groups IB, IIB, VB, VIB, VIIB and VIII of the periodic table, at least one ligand and at least one organometallic reducing agent, said contact resulting in a conversion of said 1,3-butadiene to primarily cis-2-butene.

### Claim 2 (depends on 1)

A process according to claim 1, characterized in that:
the transition metal salt is selected from halides, acetylacetonates and carboxylates of organic acids containing 2 to 25 carbon atoms;
the reducing agent is selected from organometallic derivatives of at least one metal selected from the group formed by lithium, sodium and aluminium;
the ligand is selected from derivatives of phosphorus, arsenic and antimony and nitrogen-containing ligands.

### Claim 3 (depends on 2)

A process according to claim 2, wherein the transistion metal salt is carboxylate selected from acetates, octoates, decanoates, naphthenates, stearates, palmitates, oleates and benzoates.

### Claim 4 (depends on 1)

A process according to claim 1, characterized in that the transition metal salt is selected from salts of metals from groups IB, IIB, VIB and VIII of the periodic table.

### Claim 5 (depends on 4)

A process according to claim 4, characterized in that the transition metal salt is selected from copper, zinc, chromium, molybdenum, iron, cobalt, nickel, ruthenium and palladium salts.

### Claim 6 (depends on 5)

A process according to claim 5, characterized in that the transition metal salt is selected from iron salts.

### Claim 7 (depends on 1)

A process according to claim 1, characterized in that the reducing agent is selected from:
organoaluminas with general formula AlRy(X)3-y, in which R is an alkyl group, X is a halide and y=1, 2 or 3;
magnesias with formula MgR2, in which R is as defined above;
aluminoxanes;
sodium borohydride; and
alkaline hydrides and their substitution derivatives comprising 1, 2 or 3 alkoxy groups.

### Claim 8 (depends on 1)

A process according to claim 1, characterized in that the ligand derived from phosphorus, arsenic or antimony is selected from ligands with general formulae:
YRmX3-m, YR3, R2Y—(CH2)nYR2, Y(OR)3 and YOR3,
in which Y=P, As or Sb, m=0, 1, 2 or 3; R=alkyl, aryl or substituted aryl; X=halogen, and n=0, 1, 2, 3 or 4.

### Claim 9 (depends on 1)

A process according to claim 1, characterized in that the nitrogen-containing ligand is selected from amines, polyamines, imidazole, substituted imidazoles, pyrrole, substituted pyrroles, pyrazoles, amide derivatives, imines, diimines and pyridine derivatives.

### Claim 10 (depends on 1)

A process according to claim 1 characterized in that a minor proportion of at least one salt of a further transition metal selected from metals from groups IB, VB, VIB, VIIB and VIII is added to the catalyst.

### Claim 11 (depends on 10)

A process according to claim 10, characterized in that the principal metal is iron and the additional metal is selected from Co, Ni, Cu, Rh, Pd, Mn, Mo, W and V.

### Claim 12 (depends on 1)

A process according to claim 1, characterized in that the catalyst composition is dissolved in at least one organic compound selected from aliphatic or aromatic hydrocarbons, ethers, esters, halogenated hydrocarbons, sulphoxides and amides.

### Claim 13 (depends on 1)

A process according to claim 1, characterized in that the catalyst composition is dissolved in at least one ionic liquid with general formula Q+A− in which Q+ represents a quaternary ammonium and/or quaternary phosphonium ion and A31 represents any anion which is capable of forming a liquid salt at low temperatures, i.e. below 90° C.

### Claim 14 (depends on 13)

A process according to claim 13, characterized in that the quaternary ammonium and/or phosphonium ion Q+ has one of the following general formulae:
NR1R2R3R4+ and PR1R2R3R4+
or one of general formulae:
R1R2N═CR3R4+ and R1R2P═CR3R4+
in which R1, R2, R3 and R4, which may be identical or different, each represent hydrogen, the cation NH4+ being excluded for NR1R2R3R4+, or a hydrocarbyl residue containing 1 to 30 carbon atoms.

### Claim 15 (depends on 13)

A process according to claim 13, characterized in that the quaternary ammonium and/or phosphonium ion Q+ derives from a nitrogen-containing or phosphorus-containing heterocycle comprising 1, 2 or 3 nitrogen or phosphorus atoms, having one of the following general formulae:
in which the cycles are constituted by 4 to 10 atoms and R1 and R2, which may be identical or different, each represent hydrogen or a hydrocarbyl residue containing 1 to 30 carbon atoms.

### Claim 16 (depends on 13)

A process according to claim 13, characterized in that the quaternary ammonium and/or phosphonium ion has one of the following formulae:
R1R2+N═CR3—R5—R3C═N+R1R2 or
R1R2+P═CR3—R5—R3C═P+R1R2
in which R1, R2 and R3, which may be identical or different, each represent hydrogen or a hydrocarbyl residue containing 1 to 30 carbon atoms and R5 an alkylene or phenylene residue.

### Claim 17 (depends on 1)

A process according to claim 1, characterized in that the mole ratio between the ligand and the transition metal salt is in the range 0.5/1 to 10/1.

### Claim 18 (depends on 1)

A process according to claim 1, characterized in that the ligand is monocoordinating and the ligand/transition metal salt mole ratio is 2/1 to 3/1.

### Claim 19 (depends on 1)

A process according to claim 1, characterized in that the ligand is bi-coordinating and the ligand/transition metal salt mole ratio is 1/1 to 1.5/1.

### Claim 20 (depends on 1)

A process according to claim 1, characterized in that the mole ratio between the reducing agent and the transition metal salt is 1/1 to 15/1.

### Claim 21 (depends on 1)

A process according to claim 1, characterized in that said catalyst composition is employed in a proportion corresponding to a proportion of metallic compounds in the reaction medium of 10 to 10000 ppm by weight.

### Claim 22 (depends on 1)

An integrated process for producing 1-butene from a 1-butene rich C4 cut, characterized in that it comprises, as the finishing step, selective hydrogenation of 1,3-butadiene carried out using a process according to claim 1 to obtain a 1,3-butadiene content of less than 10 ppm by weight.

### Claim 23 (depends on 1)

A process according to claim 1 conducted under conditions resulting in a selectivity of cis-2-butene of over 98% for an 80% 1,3-butadiene conversion.

### Claim 24 (depends on 23)

A process according to claim 23 wherein the catalyst comprises an iron salt and the ligand is an imino compound.