PROCESS FOR HYDRODEOXYGENATION AND PROCESS FOR UPGRADING OF PYROLYSIS OIL RESULTING FROM BIOMASS, WHICH ARE CAPABLE OF OPERATING CONTINUOUSLY

• US 20130255138A1
• Filed: 11/21/2011
• Published: 10/03/2013
• Est. Priority Date: 11/19/2010
• Status: Active Grant

• Current Assignee: Total Raffinage France SAS (Totalenergies Se)
• Original Assignee: Total Raffinage Marketing (Cook Composites and Polymers)
• Inventors: Mayeur, Vincent, Preau, Alexandre
• Granted Patent: US 9,193,919 B2
• Time in Patent Office: Days
• US Class Current: 44/307
• CPC Class Codes: B01J 2208/00061 of the reactants
• CPC Class Codes: B01J 2208/00548 Flow
• CPC Class Codes: B01J 2208/025 Two or more types of catalyst
• CPC Class Codes: B01J 8/0453 the beds being superimposed one above the other
• CPC Class Codes: B01J 8/0457 the beds being placed in separate reactors
• CPC Class Codes: B01J 8/0496 Heating or cooling the reactor
• CPC Class Codes: C10G 1/02 by distillation
• CPC Class Codes: C10G 2300/1014 of vegetal origin
• CPC Class Codes: C10G 2300/4006 Temperature
• CPC Class Codes: C10G 2300/4081 Recycling aspects
• CPC Class Codes: C10G 2300/42 Hydrogen of special source or of special composition
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 Diesel oil
• CPC Class Codes: C10G 2400/08 Jet fuel
• CPC Class Codes: C10G 3/42 Catalytic treatment
• CPC Class Codes: C10G 3/45 containing iron group metals or compounds thereof
• CPC Class Codes: C10G 3/46 in combination with chromium, molybdenum, tungsten metals or compounds thereof
• CPC Class Codes: C10G 3/47 containing platinum group metals or compounds thereof
• CPC Class Codes: C10G 3/48 further characterised by the catalyst support
• CPC Class Codes: C10G 3/49 containing crystalline aluminosilicates, e.g. molecular sieves
• CPC Class Codes: C10G 3/50 : in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• CPC Class Codes: C10G 3/60 : Controlling or regulating the processes
• CPC Class Codes: C10G 45/72 : Controlling or regulating
• CPC Class Codes: C10L 1/00 : Liquid carbonaceous fuels
• CPC Class Codes: Y02P 30/20 : using bio-feedstock

Abstract

The invention relates to a process for hydrodeoxygenation (HDO) of pyrolysis oil and also to a process for upgrading of pyrolysis oil implementing said HDO process, and also to processing of the aqueous phase resulting from the HDO by steam pre-reforming and then steam reforming.

Claims

1. A process for the catalytic hydrodeoxygenation (HDO) of biomass pyrolysis oil and/or of the ligneous organic phase resulting from the phase separation of biomass pyrolysis oil to which water has been added, comprising a plurality of catalytic beds arranged in series and distributed in one or more reactors which is/are equipped with means for controlling the temperature, and characterized by:

the injection of the pyrolysis oil at the top of the 1^st catalytic bed,

the fractional injection of the hydrogen;

the 1^st injection of hydrogen is carried out at the top of the 1^st catalytic bed,

the other injection or injections of H₂ being carried out between 2 catalytic beds and being chosen so that the difference between 2 successive H₂ injection temperatures does not exceed 50°

C., Δ

Tmax≦

50°

C., with Δ

Tmax=[rank (n+1) H₂ injection temperature]−

[rank (n) H₂ injection temperature],

the separation of the liquid effluents at the outlet of the final catalytic bed into a liquid phase and an organic phase, it being possible for a portion of the organic phase optionally to be recycled in the reactor, for example to be reinjected with the pyrolysis oil,

preferably, the amount of hydrogen injected into a bed is equal to the stoichiometric amount necessary to achieve a target Δ

T in this bed,

and/or, preferably, the amount of hydrogen injected at the top of the 1^st bed is such that the water of the pyrolysis oil is not evaporated.

2. The process as claimed in claim 1, characterized in that the pressure in the HDO reactor or reactors is between 5 and 20 MPa preferably between 10 and 15 MPa.

3. The process as claimed in claim 1, characterized in that the inlet temperature of the 1^st catalytic bed is between 120 and 180°

C., preferably between 140 and 160°

C.

4. The process as claimed in claim 1, characterized in that the variation in temperature Δ

Tmax between two catalytic beds is obtained by controlling the flow rate and/or temperature conditions of the H₂ streams injected between said catalytic beds.

5. The process as claimed in claim 1, characterized in that the HDO catalyst or catalysts of the catalytic beds, which are identical or different, are chosen from the catalysts comprising at least one of the metals from Group VI, VII or VIII (Ni, Cr, Mo, W, Co, Rh, Ir, Ru, Pt, Pd, Re, and the like), the metal or metals, alone or as a mixture, preferably being deposited on and/or dispersed over supports, such as alumina, silica/alumina, cerium, zirconium, carbon, titanium or zeolite (zeolite beta, zeolite Y, zeolites of MFI type, mordenite, silicalite, SM3 and/or faujasite).

6. The HDO process as claimed in claim 1, which operates continuously, preferably with a Δ

Tmax≦

20 to 30°

C. between each H₂ injection.

7. The extensive (conversion >

90%) or total HDO process as claimed in claim 1, characterized in that it comprises at least 4H₂ injections, preferably at least 5H₂ injections and advantageously at least 6H₂ injections.

8. The process as claimed in claim 7, characterized in that the outlet temperature of the final catalytic bed is between 320 and 380°

C.

9. The partial (conversion between 10 and 90%) HDO process as claimed in claim 1, characterized in that the outlet temperature of the final catalytic bed is between 180 and 320°

C.

10. A process for the preparation of liquid fuels of renewable or partially renewable origin, of gasoline, jet fuel, kerosene, diesel fuel, domestic heating oil and/or naphtha type, based on biomass pyrolysis oil and/or on the organic phase resulting from the phase separation of biomass pyrolysis oil to which water has been added, which has/have been subjected to an HDO treatment as defined in claim 7, and optionally on fossil or mineral base(s), such as refinery petroleum base(s).

11. A process for the preparation of chemical intermediates based on pyrolysis oil which has been subjected to a partial HDO treatment as defined in claim 9.

12. A process for upgrading pyrolysis oil and/or the ligneous organic phase resulting from the phase separation of biomass pyrolysis oil to which water has been added to give liquid fuels, comprising the following stages:

extensive or total HDO of pyrolysis oil and/or of the ligneous organic phase resulting from the phase separation of biomass pyrolysis oil to which water has been added, according to the HDO process as defined above (1^st stage), followed by separation of the liquid effluent obtained into a light aqueous fraction and a heavy organic fraction;

prereforming the “

light”

aqueous fraction and treating the “

light”

aqueous fraction in an SMR unit in order to produce hydrogen;

hydrotreating said “

heavy”

organic fraction resulting from the HDO, optionally in combination with conventional refinery fuel bases.