Olefin metathesis method using a catalyst containing aluminium and molybdenum incorporated by means of at least two precursors

• US 10,322,984 B2
• Filed: 07/26/2016
• Issued: 06/18/2019
• Est. Priority Date: 07/31/2015
• Status: Expired due to Fees

• Current Assignee: IFP Energies Nouvelles
• Original Assignee: IFP Energies Nouvelles
• Inventors: Bonduelle, Audrey, Chaumonnot, Alexandra, Delcroix, Damien, Vallee, Christophe
• Primary Examiner(s): Louie, Philip Y
• Application Number:
  US15/749,368
• Publication Number:
  US 20180230071A1
• Time in Patent Office: 1,057 Days
• Field of Search: None
• CPC Class Codes: B01J 21/02 Boron or aluminium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 23/002 Mixed oxides other than spinels, e.g. perovskite
• CPC Class Codes: B01J 23/28 Molybdenum
• CPC Class Codes: B01J 23/882 and cobalt
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/31 Aluminium
• CPC Class Codes: B01J 2523/51 Phosphorus
• CPC Class Codes: B01J 2523/68 Molybdenum
• CPC Class Codes: B01J 2523/845 Cobalt
• CPC Class Codes: B01J 27/19 Molybdenum
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/635 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/647 2-50 nm
• CPC Class Codes: B01J 37/0018 Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• CPC Class Codes: B01J 37/0205 in several steps
• CPC Class Codes: B01J 37/0236 Drying, e.g. preparing a suspension, adding a soluble salt and drying
• CPC Class Codes: B01J 37/088 Decomposition of a metal salt
• CPC Class Codes: C07C 11/04 Ethylene
• CPC Class Codes: C07C 11/06 Propene
• CPC Class Codes: C07C 11/08 with four carbon atoms
• CPC Class Codes: C07C 2521/02 : Boron or aluminium; Oxides or hydroxides thereof
• CPC Class Codes: C07C 2521/08 : Silica
• CPC Class Codes: C07C 2523/28 : Molybdenum
• CPC Class Codes: C07C 6/04 : at a carbon-to-carbon double bond
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

The invention relates to a process for the metathesis of olefins implemented with a catalyst comprising a mesoporous matrix and at least the elements molybdenum and aluminum, said elements being incorporated into said matrix by means of at least two precursors of which at least one precursor contains molybdenum and at least one precursor contains aluminum.

Claims

1. A process for the metathesis of olefins, comprising bringing the olefins into contact with a catalyst comprising a mesoporous matrix and at least the elements molybdenum and aluminium, said elements being incorporated into said matrix using at least two precursors of which at least one precursor contains molybdenum and at least one precursor contains aluminium, in which the catalyst is prepared by dry impregnation according to a process comprising:

a) solubilizing of the molybdenum-containing precursor and the aluminium-containing precursor in a volume of solution corresponding to the pore volume of a preformed mesoporous matrix based on oxide,

b) impregnating the preformed mesoporous matrix based on oxide with the solution obtained in a), optionally maturating a solid thus obtained,

c) optionally drying, calcining and/or steam treating a solid obtained at the end of b), at a pressure greater than or equal to 0.1 MPa at a temperature of 50°

C. to 1000°

C., and

d) thermally activating a solid obtained at the end of c), at a pressure greater than or equal to 0.1 MPa and a temperature of 100°

C. to 1000°

C.

2. The process according to claim 1 in which the molybdenum-containing precursor is a coordination complex based on molybdenum and/or polyoxometallate based on molybdenum and/or a (thio)molybdate.

3. The process according to claim 1 in which the molybdenum-containing precursor of the coordination complex type based on molybdenum has formula (I)

Mo_m(═

Y)_n(≡

N)_n′

(X)_o(═

CR₂)_r 

 

(I)

in which,

the Y groups, identical to or different from each other, are O, S and or NR′

,

the X groups, identical to or different from each other, are halides, chlorate, bromate, iodate, nitrate, sulphate, hydrogen sulphate, alkylsulphate, thiosulphate, carbonate, hydrogen carbonate, phosphate, hydrogen phosphate, dihydrogen phosphate, substituted or unsubstituted alkyl, cycloalkyl or aryl groups, substituted or unsubstituted cyclopentadienyl groups, alkoxy, aryloxy, siloxy, amide, hydrido, nitro, carboxylate, acetylacetonate, sulphonate, β

-diketiminate, iminopyrrolure, amidinate, borate, cyanide, cyanate, thiocyanate or NR₂—

CS₂⁻

groups,

the R and R′

groups, identical to or different from each other, are alkyl, aryl alkoxy or aryloxy groups,

m is equal to 1 or 2,

n is 0 to 4,

n′

is 0 to 2,

o is 0 to 10,

r is 0 to 2, and

n+n′

+o+r is greater than or equal to 1.

4. The process according to claim 1 in which the molybdenum-containing precursor is a polyoxometallate based on molybdenum of formula (II)

(X_xMo_mM_bO_yH_h)^q−

.nH₂O 

 

(II)

in which,

x is greater than or equal to 0,

m is greater than or equal to 2,

b is greater than or equal to 0,

y is greater than or equal to 7,

h is 0 to 12,

q is 1 to 20,

n is 0 to 200, and

x, m, b, y, h, n and q being integers, X being phosphorus, silicon or boron, M being aluminium, zinc, nickel, cobalt, tungsten, vanadium, niobium, tantalum, iron or copper.

5. The process according to claim 4 in which the polyoxometallate is an isopolyanion based on molybdenum in which the subscript x of the element X is equal to 0.

6. The process according to claim 4 in which the polyoxometallate is a heteropolyanion that is a Strandberg heteropolyanion of formula X₂Mo₅O₂₃H_h^q−

.nH₂O, an Anderson heteropolyanion of formula XMo₆O₂₄H_h^q−

.nH₂O, a Keggin heteropolyanion of formula XMo₁₂O₄₀H_h^q−

.nH₂O, a lacunary Keggin heteropolyanion of formula XMo₁₁O₃₉H_h<sup>−

q</sup>.nH₂O, a lacunary Keggin heteropolyanion of formula XMo₉O₃₄H_h^q−

.nH₂O, a Dawson heteropolyanion of formula X₂Mo₁₈O₆₂H_h^q−

.nH₂O, or a Preyssler heteropolyanion of formula X₅Mo₃₀O₁₁₀H_h^q−

.nH₂O.

7. The process according to claim 4 in which the polyoxometallate is a heteropolyanion that is a Strandberg heteropolyanion of formula X₂Mo₄CoO₂₃H_h^q−

.nH₂O, an Anderson heteropolyanion of formula XMo₅CoO₂₄H_h^q−

.nH₂O, a Keggin heteropolyanion of formula XMo₁₁CoO₄₀H_h^q−

.nH₂O, a lacunary Keggin heteropolyanion of formula XMo₁₀CoO₃₉H_h^q−

.nH₂O, a lacunary Keggin heteropolyanion of formula XMo₈CoO₃₄H_h^q−

.nH₂O, a Dawson heteropolyanion of formula X₂Mo₁₇CoO₆₂H_h^q−

.nH₂O, or a Preyssler heteropolyanion of formula X₅Mo₂₉CoO₁₁₀H_h^q−

.nH₂O.

8. The process according to claim 1 in which the molybdenum-containing precursor is a (thio)molybdate of formula (III)

C_c(MoY₄)_z 

 

(III)

in which

C represents an organic or inorganic cation,

the Y groups, identical to or different from each other, are O and or S,

c is 1 to 4, and

z is 1 to 10.

9. The process according to claim 1 in which the aluminium-containing precursor is a coordination complex based on aluminium and/or an aluminium salt and/or a heteropolyanion salt based on aluminium and/or a colloidal solution of alumina.

10. The process according to claim 1 in which the aluminium-containing precursor is a coordination complex based on aluminium of formula (IV)

Al_nR_m.xH₂O 

 

(IV)

in which,

n is 1 to 3,

m is 1 to 3,

x is 0 to 200, and

the R groups are identical or different from each other, and are hydrogen, a halides, chlorate, bromate, iodate, nitrate, sulphate, hydrogen sulphate, alkylsulphate, thiosulphate, carbonate, hydrogen carbonate, phosphate, hydrogen phosphate, dihydrogen phosphate, a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl or aryl group, a substituted or unsubstituted cyclopentadienyl group, or a hydroxy, alkoxy, aryloxy, carboxylate, nitrate, acetylacetonate, sulphonate, or perchlorate group.

11. The process according to claim 1 in which the aluminium-containing precursor is an aluminium salt of formula (V)

[Al_nR_m]⁻

[C]⁺.nH₂O 

 

(V)

in which,

n is 1 to 3,

m is 1 to 3,

x is 0 to 200,

the R groups are identical to or different from each other, and are hydrogen, an oxo group, a halides, a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl or aryl group, a substituted or unsubstituted cyclopentadienyl group, or a hydroxy, alkoxy, aryloxy, carboxylate, sulphonate, nitrate, acetylacetonate, or perchlorate group, and

C is hydrogen, an alkali, an alkaline-earth element, a transition metal, a post-transition metal, a rare earth, or an ammonium or phosphonium cation.

12. The process according to claim 1 in which the aluminium-containing precursor is a heteropolyanion salt based on aluminium of formula (VI)

(Al_aM1_mM2_bX_xO_yH_h)^q−

(C^r+)_c.nH₂O 

 

(VI)

in which,

a is greater than 0,

m is greater than or equal to 1,

b is greater than or equal to 0,

x is greater than or equal to 0,

y is greater than or equal to 10,

h is 0 to 12,

q is 0 to 20,

r is 0 to 20,

c is 0 to 20,

n is 0 to 200,

x, m, y, h, n and q being integers, X being phosphorus, silicon or boron, M1 and M2, identical to or different from each other, being aluminium, zinc, nickel, cobalt, molybdenum, tungsten, vanadium, niobium, tantalum, iron or copper, and

C represents one or more atoms, identical or different, hydrated or non-hydrated, capable of existing in the cationic form, hydrogen, the alkali, alkaline-earth elements, transition metals, post-transition metals and rare earths, in hydrated or non-hydrated forms, selected from the oxygen-containing and/or nitrogen-containing and/or phosphorus-containing organic cations.

13. The process according to claim 1 in which the mesoporous matrix is a matrix based on the oxide of at least one element X that is silicon, titanium, zirconium, magnesium, lanthanum, cerium or mixtures thereof.

14. A process according to claim 1 in which the metathesis reaction is carried out at a temperature of 0 to 500°

C.

15. The process according to claim 14 in which the olefins are linear olefins of formula R¹R²C═

CR³R⁴, where R¹, R², R³ and R⁴, identical or different, are hydrogen or a hydrocarbyl radical of 1 to 20 carbon atoms, or olefins with a cyclic structure, the ring having 3 to 20 carbon atoms.

16. The process according to claim 1 in which the metathesis reaction is the cross-metathesis reaction of ethylene with 2-butene, or the reverse reaction converting propylene to a mixture of ethylene and 2-butene.

17. A process for the metathesis of olefins, comprising bringing the olefins into contact with a catalyst comprising a mesoporous matrix and at least the elements molybdenum and aluminium, said elements being incorporated into said matrix using at least two precursors of which at least one precursor contains molybdenum and at least one precursor contains aluminium, in which the catalyst is prepared by a process comprising the following stages:

a′

) solubilizing of the molybdenum-containing precursor in a volume of solution corresponding to the pore volume of a preformed mesoporous matrix based on oxide,

b′

) impregnating of the preformed mesoporous matrix based on oxide with the solution obtained in a), optionally maturing a solid thus obtained,

c′

) drying to remove impregnation solvent from solution a′

),

d′

) solubilizing aluminium-containing precursor in a volume of solution corresponding to the pore volume of solid obtained in c′

),

e′

) impregnating a solid obtained in c′

) with a solution obtained in d′

), optionally maturing a solid thus obtained,

f′

) optionally drying, calcining and/or steam treating a solid obtained at the end of stage e′

), at a pressure greater than or equal to 0.1 MPa at a temperature of 50°

C. to 1000°

C., and

g′

) thermally activating a solid obtained at the end of f′

), at a pressure greater than or equal to 0.1 MPa, in a temperature of 100°

C. to 1000°

C.

18. A process for the metathesis of olefins, comprising bringing the olefins into contact with a catalyst comprising a mesoporous matrix and at least the elements molybdenum and aluminium, said elements being incorporated into said matrix using at least two precursors of which at least one precursor contains molybdenum and at least one precursor contains aluminium, in which the catalyst is prepared by impregnation in excess solution according to a process comprising:

a″

) solubilizing the molybdenum-containing precursor and the aluminium-containing precursor in a volume of solution, corresponding to between 1.5 and 20 times the pore volume of the preformed mesoporous matrix based on oxide,

b″

) impregnating the preformed mesoporous matrix based on oxide, with the solution obtained in a″

), filtration and recovery of the solid, optionally maturing of a solid thus obtained,

c″

) optionally drying, calcining and/or steam treating of a solid obtained at the end of b″

) at a pressure greater than or equal to 0.1 MPa at a temperature of 50°

C. to 1000°

C., and

d″

) thermally activating of a solid obtained at the end of c″

) at a pressure greater than or equal to 0.1 MPa at a temperature of 100°

C. to 1000°

C.