Process for direct hydorliquefaction of biomass comprising two stages of ebullating bed hydroconversion

• US 8,623,102 B2
• Filed: 01/11/2011
• Issued: 01/07/2014
• Est. Priority Date: 01/12/2010
• Status: Active Grant

• Current Assignee: IFP Energies Nouvelles
• Original Assignee: IFP Energies Nouvelles
• Inventors: Quignard, Alain, Weiss, Wilfried
• Primary Examiner(s): Singh, Prem C
• Assistant Examiner(s): GRAHAM, CHANTEL LORAN
• Application Number:
  US13/004,304
• Publication Number:
  US 20110167713A1
• Time in Patent Office: 1,092 Days
• Field of Search: 585/240, 585/252, 208/27, 443/07, 443/08, 554/141, 554/144, 554/145
• US Class Current: 44/307
• CPC Class Codes: B01J 23/40 of the platinum group metals
• CPC Class Codes: B01J 23/652 Chromium, molybdenum or tungsten
• CPC Class Codes: B01J 23/75 Cobalt
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 23/85 Chromium, molybdenum or tungsten
• CPC Class Codes: B01J 23/883 and nickel
• CPC Class Codes: B01J 37/20 Sulfiding
• CPC Class Codes: C10G 1/08 with moving catalysts
• CPC Class Codes: C10G 1/083 in the presence of a solvent
• CPC Class Codes: C10G 2300/1014 of vegetal origin
• CPC Class Codes: C10G 2300/4006 Temperature
• CPC Class Codes: C10G 2300/4012 Pressure
• CPC Class Codes: C10G 2300/4018 Spatial velocity, e.g. LHSV, WHSV
• CPC Class Codes: C10G 2300/44 Solvents
• 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 3/45 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 3/50 : in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• CPC Class Codes: C10G 3/56 : suspended in the oil, e.g. slurries, ebullated beds
• CPC Class Codes: Y02E 50/10 : Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02E 50/30 : Fuel from waste, e.g. synthetic alcohol or diesel
• CPC Class Codes: Y02P 30/20 : using bio-feedstock

Abstract

A process for direct hydroliquefaction of biomass selected from algae, lignocellulosic biomass and/or of one or more constituents of lignocellulosic biomass selected from the group comprising cellulose, hemicellulose and/or lignin for producing fuel bases comprising two successive hydroconversion stages under high hydrogen pressure in ebullating bed reactors. Hydroconversion takes place in the presence of a supported catalyst of the type for hydroconversion of petroleum residue and a suspension composed of the biomass and a solvent, preferably a hydrogen donor solvent and preferably recycled from the process. The biomass can undergo a pretreatment of drying and/or roasting and/or grinding and/or demineralization prior to hydroliquefaction.

Claims

1. Process for hydroliquefaction of biomass selected from algae, lignocellulosic biomass and/or of one or more constituents of lignocellulosic biomass selected from the group comprising cellulose, hemicellulose and/or lignin for producing fuel bases comprising

a) a stage of preparation of a suspension of particles of biomass in a solvent,

b) a first stage of hydroconversion in the presence of hydrogen of said suspension in at least one reactor containing an ebullating bed catalyst and operating at a temperature comprised between 300°

C. and 440°

C., at a total pressure comprised between 15 and 25 MPa, at an hourly mass velocity comprised between 0.1 and 5 h<sup>−

1</sup> and at a hydrogen/feed ratio comprised between 0.1 and 2 Nm³/kg,

c) a second stage of hydroconversion in the presence of hydrogen of at least a proportion of effluent obtained in stage b) in at least one reactor containing an ebullating bed catalyst and operating at a temperature comprised between 350°

C. and 470°

C., at a total pressure comprised between 15 and 25 MPa, at an hourly mass velocity comprised between 0.1 and 5 h<sup>−

1</sup> and a hydrogen/feed ratio comprised between 0.1 and 2 Nm³/kg, and wherein the temperature of the second hydroconversion stage is at least 10°

C. higher than that of the first hydroconversion stage.

2. Process according to claim 1, characterized in that the first hydroconversion stage takes place at a temperature between 325°

C. and 375°

C. and at a total pressure comprised between 16 and 20 MPa, and in that the second hydroconversion stage takes place at a temperature comprised between 350°

C. and 425°

C. and at a total pressure comprised between 16 and 20 MPa.

3. Process according to claim 1, characterized in that the lignocellulosic biomass and/or one or more constituents of the lignocellulosic biomass selected from the group comprising cellulose, hemicellulose and/or lignin undergo a pretreatment comprising at least one of the following stages:

a) a drying stage carried out at a temperature below 250°

C., and/or a stage of roasting, said roasting being carried out at a temperature comprised between 200 and 300°

C., in the absence of air,

b) a grinding stage.

4. Process according to claim 1, wherein the biomass is algae in which the algae are subjected to a pre-treatment comprising at least one of the following stages:

a) a demineralization stage,

b) a drying stage carried out at a temperature below 250°

C.,

c) a grinding stage.

5. Process according to claim 1, characterized in that the particles of biomass have a water content of 1 to 50%, and a particle size less than 600 microns.

6. Process according to claim 1, characterized in that said solvent comprises vacuum distillate, and optionally atmospheric distillate, the solvent/biomass weight ratio being from 0.1 to 3, said solvent being a solvent obtained from a separation stage carried out after the two hydroconversion stages, said solvent being recycled upstream of the two hydroconversion stages.

7. Process according to claim 1, characterized in that said biomass is co-processed with a feed selected from petroleum residues, petroleum crudes, synthetic crudes, topped petroleum crudes, deasphalted oils, resins from deasphalting, asphalts from deasphalting, derivatives from petroleum processing, bituminous sands or their derivatives, bituminous shales or their derivatives, coal or liquefied products obtained from coal by hydroliquefaction, hydrocarbon and/or polymer industrial waste, household organic or plastic waste, vegetable or animal oils and fats, tars and residues that can be upgraded with difficulty or not at all, originating from gasification of biomass, coal or petroleum residues, charcoal, pyrolysis oil or mixtures of said feeds.

8. Process according to claim 1, characterized in that said catalyst comprises a group VIII metal selected from the group comprising Ni, Pd, Pt, Co, Rh and/or Ru, optionally a group VIB metal selected from the group Mo and/or W, on an amorphous mineral support selected from the group comprising alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals.

9. Process according to claim 1, characterized in that the effluent obtained at the end of the first hydroconversion stage is subjected to separation of the light fraction and at least a proportion, preferably all, of the residual effluent is treated in the second hydroconversion stage.

10. Process according to claim 1, characterized in that the effluent obtained at the end of the second hydroconversion stage undergoes a separation stage for separating a gaseous phase, an aqueous phase, at least one light fraction of liquid hydrocarbons of the naphtha, kerosene and/or diesel type, a vacuum gas oil heavy fraction of hydrocarbons, a vacuum residue fraction and a solid fraction that can be in the vacuum residue.

11. Process according to claim 10, wherein the separation stage provides the vacuum gas oil heavy fraction of hydrocarbons which is then recycled wholly or partly to the stage (a) for preparation of a suspension.

12. Process according to claim 10, characterized in that at least partially the light fraction(s) and/or the heavy fraction obtained after separation undergo a hydrotreating and/or hydrocracking stage.

13. Process according to claim 1, characterized in that at least a proportion of the effluent obtained at the end of the second hydroconversion stage directly undergoes a hydrotreating and/or hydrocracking stage without intermediate decompression.

14. Process according to claim 1, characterized in that the spent catalyst from the second hydroconversion stage is passed wholly or partly directly to the first hydroconversion stage.

15. A process according to claim 1, wherein said solvent in step (a) is a hydrogen donor solvent.

16. A process according to claim 1, further comprising fractionating the resultant hydroliquefaction of biomass output to yield a hydrogen donor solvent, and passing said hydrogen donor solvent to stage (a), facilitating passage of said suspension to said reaction zone in step (b), and by hydrogen transfer to resultant products, ensuring a conversion to liquid by minimizing solids and gases formed in the reaction zone.

17. A process according to claim 3, wherein the drying stage in step (a) is conducted at below 200°

C. and the roasting is conducted at between 225°

C. and 275°

C.

18. A process according to claim 5, wherein the drying stage is conducted at a temperature below 200°

C.

19. A process according to claim 5, wherein the particles of biomass have a water content of 5 to 10% and a particle size less than 150 microns.

20. A process according to claim 6, wherein said solvent comprising vacuum gas oils (VGO).

21. A process according to claim 20, said solvent being obtained from a separation stage carried out after the two hydroconversion stages, said solvent being recycled upstream of the two hydroconversion stages.

22. A process according to claim 1, wherein said solvent in step (a) is a hydrogen donor solvent obtained by a step comprising fractionating the resultant hydroliquefaction of biomass output to yield said hydrogen donor solvent, and passing said hydrogen donor solvent to stage (a), facilitating passage of said suspension to said reaction zone in step (b), and by hydrogen transfer to resultant products, ensuring a conversion to liquid by minimizing solids and gases formed in the reaction zone, wherein the drying stage in step (a) is conducted at below 200°

C. and the roasting is conducted at between 225°

C. and 275°

C.,

wherein the particles of biomass have a water content of 5 to 10% and a particle size less than 150 microns,

wherein said solvent comprises vacuum gas oils (VGO),

said solvent being obtained from a separation stage carried out after the two hydroconversion stages (b) and (c), said solvent being recycled upstream of the two hydroconversion stages.

23. A process according to claim 1, wherein the biomass comprises green algae suspended in tetralin and wherein the catalyst is presulfided NiMo/Al₂O₃.