Process for the conversion of carbon-based material by a hybrid route combining direct liquefaction and indirect liquefaction in the presence of hydrogen resulting from non-fossil resources

• US 9,163,180 B2
• Filed: 12/06/2012
• Issued: 10/20/2015
• Est. Priority Date: 12/07/2011
• Status: Active Grant

• Current Assignee: IFP Energies Nouvelles
• Original Assignee: IFP Energies Nouvelles
• Inventors: Marion, Pierre, Quignard, Alain, Weiss, Wilfried
• Primary Examiner(s): Boyer, Randy
• Application Number:
  US13/706,905
• Publication Number:
  US 20130149767A1
• Time in Patent Office: 1,048 Days
• US Class Current: 1/1
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/025 containing a partial oxidation step
• CPC Class Codes: C01B 2203/0415 Purification by absorption in liquids
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/062 Hydrocarbon production, e.g. Fischer-Tropsch process
• CPC Class Codes: C01B 3/36 using oxygen or mixtures containing oxygen as gasifying agents
• CPC Class Codes: C10G 1/002 in combination with oil conversion- or refining processes
• CPC Class Codes: C10G 1/065 in the presence of a solvent
• CPC Class Codes: C10G 1/08 with moving catalysts
• CPC Class Codes: C10G 2/32 with the use of catalysts
• CPC Class Codes: C10G 2/332 of the iron-group
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2300/1022 Fischer-Tropsch products
• CPC Class Codes: C10G 2300/4043 Limiting CO2 emissions
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 Diesel oil
• CPC Class Codes: C10G 45/64 containing crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 47/16 Crystalline alumino-silicate carriers
• CPC Class Codes: C10G 47/20 the catalyst containing other metals or compounds thereof
• CPC Class Codes: C10G 65/14 plural parallel stages only
• CPC Class Codes: C10J 2300/093 : Coal
• CPC Class Codes: C10J 2300/0989 : Hydrocarbons as additives to gasifying agents to improve caloric properties
• CPC Class Codes: C10J 2300/1618 : Modification of synthesis gas composition, e.g. to meet some criteria
• CPC Class Codes: C10J 2300/1659 : to liquid hydrocarbons Fischer-Tropsch process C10G2/00
• CPC Class Codes: C10J 2300/1671 : with the production of electricity
• CPC Class Codes: C10J 2300/1684 : with electrolysis of water
• CPC Class Codes: C10J 2300/1846 : Partial oxidation, i.e. injection of air or oxygen only
• CPC Class Codes: C10J 3/00 : Production of combustible gases containing carbon monoxide from solid carbonaceous fuels destructive distillation processes C10B
• CPC Class Codes: C10K 1/005 : Carbon dioxide
• CPC Class Codes: C10K 3/026 : Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
• CPC Class Codes: C10K 3/06 : by mixing with gases
• CPC Class Codes: C25B 1/04 : by electrolysis of water
• CPC Class Codes: Y02E 50/30 : Fuel from waste, e.g. synthetic alcohol or diesel
• CPC Class Codes: Y02E 60/36 : Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02P 20/00 : Technologies relating to chemical industry
• CPC Class Codes: Y02P 20/133 : Renewable energy sources, e.g. sunlight
• CPC Class Codes: Y02P 20/145 : the feedstock being materials of biological origin
• CPC Class Codes: Y02P 30/00 : Technologies relating to oil refining and petrochemical industry
• CPC Class Codes: Y02P 30/20 : using bio-feedstock

Abstract

A process for the conversion of carbon-based material to fuel bases by a hybrid route combining direct ebullent bed liquefaction and indirect liquefaction by gasification followed by a Fischer-Tropsch synthesis, including a stage of production of hydrogen resulting from non-fossil resources and a reverse water gas reaction stage. This process makes it possible to limit emissions of greenhouse gases.

Claims

1. Process for the conversion of carbon-based material to fuel bases, comprising the following stages:

a) liquefaction of at least a portion of the said carbon-based material in the presence of hydrogen in at least one reactor comprising a supported catalyst as an ebullated bed,

b) separation of the effluent obtained on conclusion of stage a) into at least one light fraction of fuel base hydrocarbons and a residual fraction comprising compounds boiling at at least 340°

C.,

c) production of hydrogen using at least one non-fossil resource, the hydrogen thus produced being at least in part introduced into the liquefaction stage a), and the subsequent reverse water gas reaction stage e) and subsequent Fischer-Tropsch reaction stage f),

d) gasification of a portion of the carbon-based material and/or of a portion at least of the residual fraction resulting from stage b) in order to produce synthesis gas comprising hydrogen, CO and CO₂, and a residual fraction from the gasification,

e) separation of a portion at least of the CO₂ present in the synthesis gas and conversion of the separated CO₂ by a reverse water gas reaction in the presence of hydrogen resulting from stage c), to produce CO and water,

f) conversion of the synthesis gas, supplemented with at least a portion of the CO resulting from stage e) and at least a portion of hydrogen resulting from stage c), by Fischer-Tropsch synthesis to give fuel bases.

2. Process according to claim 1, in which the said non-fossil resource is water, hydrochloric acid, hydrogen chloride, hydrogen sulphide and/or biomass.

3. Process according to claim 2, in which the production of hydrogen comprises the decomposition of water by electrolysis, by high-temperature electrolysis, by thermochemical cycles and/or by microorganisms.

4. Process according to claim 2, in which the production of hydrogen comprises the electrolysis of hydrochloric acid and/or the reaction of hydrogen chloride with cerium dioxide.

5. Process according to claim 2, in which the production of hydrogen comprises the decomposition of hydrogen sulphide by thermal treatment and/or by reaction with metal oxides.

6. Process according to claim 2, in which the production of hydrogen comprises biomass gasification.

7. Process according to claim 1, in which the energy supplying the production of hydrogen is a non-fossil energy chosen from the group formed by nuclear energy, photovoltaic solar energy, low-temperature solar thermal energy, high-temperature solar thermal energy, wind energy, water power or hydroelectricity, marine energy sources, geothermal energy and/or biomass, alone or as a combination of two or more of them in equal or different proportions.

8. Process according to claim 1, in which the said carbon-based material is a feedstock chosen from the group formed by coal, biomass, algae, feedstocks resulting from oil and/or from the refining of oil, products resulting from the thermochemical or hydrothermal conversion of these feedstocks, hydrocarbon waste, industrial polymers, organic waste and/or household plastics, alone or as a mixture of two or more of them in equal or different proportions.

9. Process according to claim 1, in which the separation stage b) makes it possible to obtain a gas phase, at least one light fraction of hydrocarbons of naphtha, kerosene and/or diesel type and at least one residual fraction comprising compounds boiling at at least 340°

C. comprising a vacuum distillate fraction and a vacuum residue fraction.

10. Process according to claim 9, in which at least a portion of the vacuum distillate fraction is recycled, in part or completely, in the liquefaction stage a).

11. Process according to claim 9, in which at least a portion of the vacuum residue fraction is sent to the gasification stage d).

12. Process according to claim 1, in which at least a portion of the residual fraction resulting from the gasification stage d) is, in part or completely, sent to the liquefaction stage a).

13. Process according to claim 1, in which a portion of the hydrogen present in the synthesis gas from stage d) is separated and sent to the liquefaction stage a).

14. Process according to claim 3, in which the oxygen necessary for the gasification of stage d) originates from the decomposition of water by electrolysis, by high-temperature electrolysis and/or by thermochemical cycles of stage c).

15. Process according to claim 3, in which the water produced during the reverse water gas reaction e) is recycled in the stage of production of hydrogen by electrolysis, by high-temperature hydrolysis and/or by thermochemical cycles of stage c).

16. Process according to claim 1, comprising at least one of the following refining stages:

b1) hydrocracking in the presence of hydrogen of at least a portion of the “

light”

fraction of hydrocarbons obtained on conclusion of stage b) in at least one reactor comprising a fixed bed hydrocracking catalyst, and separation of the effluent obtained on conclusion of the hydrocracking into at least one liquid fraction comprising naphtha, kerosene and/or diesel and, optionally, a heavy fraction comprising vacuum gas oil,

f1) hydrocracking/hydroisomerization in the presence of hydrogen of at least a portion of the effluent from the Fischer-Tropsch synthesis in at least one reactor comprising a hydrocracking and/or hydroisomerization catalyst,

and separation of the effluent obtained on conclusion of the hydrocracking/hydroisomerization into at least one liquid fraction comprising naphtha, kerosene and/or diesel and, optionally, a heavy fraction,

c) final mixing of the liquid fractions comprising naphtha, kerosene and/or diesel resulting from stages b1) and f1).

17. Process according to claim 1, in which at least a portion of the “

light”

fraction of hydrocarbons obtained on conclusion of stage b) and at least a portion of the effluent from the Fischer-Tropsch synthesis of stage f) are sent to a common hydrocracking stage.

18. Process according to claim 17, in which the catalyst of the common hydrocracking stage comprises at least one metal from Group VIII chosen from the group formed by Ni and Co and at least one metal from Group VIb chosen from the group Mo and W, on a support of amorphous and/or zeolitic silica/alumina type.

19. Process according to claim 17, in which the common hydrocracking stage is carried out at a temperature of between 250°

C. and 480°

C., under a pressure between 2 and 25 MPa, at the space velocity of between 0.1 and 20 h<sup>−

1</sup>, and the amount of hydrogen introduced is such that the ratio by volume of hydrogen to hydrocarbons is between 80 and 5000 Sm³/m³.