Flexible process for transformation of ethanol into middle distillates implementing a homogeneous catalytic system and a heterogeneous catalytic system

Patent metadata

Field	Value
Publication number	US-9290704-B2
Application number	US-201113102384-A
Country	US
Kind code	B2
Filing date	May 6, 2011
Priority date	May 6, 2010
Publication date	Mar 22, 2016
Grant date	Mar 22, 2016

Abstract

The invention describes a process for the production of middle distillate hydrocarbon bases from an ethanol feedstock that is produced from a renewable source that is obtained from biomass, comprising a stage for purification of said feedstock, a stage for dehydration of said purified feedstock into an effluent that is for the most part ethylene and comprises water, at least one stage for separating water, a first stage for oligomerization of the effluent that is for the most part ethylene into at least one olefinic effluent that comprises at least 80% by weight of olefins that have four or more carbon atoms, in the presence of a homogeneous catalyst that comprises at least one bivalent nickel compound, whereby a second oligomerization stage produces middle distillate hydrocarbon bases in the presence of an amorphous or zeolitic catalyst that has at least pore openings that contain 10 or 12 oxygen atoms, producing middle distillate hydrocarbon bases, and a fractionation stage.

First claim

The invention claimed is:

1. A process for the production of a kerosene hydrocarbon base from an ethanol feedstock that is produced from a renewable source that is obtained from biomass, said process comprising:
a) a stage for purification of said ethanol feedstock,
b) a stage for dehydration of the purified ethanol feedstock obtained from purification stage a) into an effluent, wherein said effluent is for the most part ethylene and also comprises water, and wherein said dehydration is conducted in the presence of an amorphous acid catalyst or a zeolitic acid catalyst,
c) at least one stage for separation of the water that is present in said effluent obtained from dehydration stage b),
d) a first stage for oligomerization of at least a portion of the effluent obtained from separation stage c) to form at least one olefinic effluent that comprises at least 80% by weight of olefins that have four or more carbon atoms, relative to the total mass of the olefins that are contained in said least one olefinic effluent, and wherein oligomerization is performed in the presence of a homogeneous catalyst that comprises at least one bivalent nickel compound, said homogeneous catalyst being soluble in a liquid phase of ethylene and its oligomerization products,
e) a second stage for oligomerization of at least a portion of the olefinic effluent obtained from first oligomerization stage d), to produce an effluent comprising middle distillate hydrocarbon bases, wherein oligomerization in the second oligomerization stage e) is performed in the presence of an amorphous catalyst, and wherein said second oligomerization stage e) is performed in at least one fixed-bed reactor operating at a temperature of between 50 and 400° C., at an absolute pressure of between 2 and 15 MPa, and at an hourly speed by weight of between 0.1 and 50 h−1, and
f) a stage for fractionation of the effluent obtained from the second oligomerization stage e) to obtain said kerosene hydrocarbon base.

2. The process according to claim 1 , wherein the homogeneous catalyst used in first oligomerization stage d) which comprises at least one bivalent nickel compound, further comprises at least one hydrocarbyl-aluminum halide, and at least one Brönsted organic acid.

3. The process according to claim 2 , wherein said at least one bivalent nickel compound is nickel octoate, nickel ethyl-2-hexanoate, nickel decanoate, nickel stearate, nickel oleate, nickel salicylate, or nickel hydroxydecanoate, taken by themselves or in a mixture.

4. The process according to claim 2 , wherein said at least one hydrocarbyl-aluminum halide is selected from among the hydrocarbyl-aluminum dihalide of the formula AlRX2, in which R is a hydrocarbyl radical and X is fluorine, chlorine, bromine or iodine, taken by themselves or in a mixture.

5. The process according to claim 2 , wherein said at least one Brönsted organic acid is a halogenocarboxylic acid of the formula RCOOH in which R is a halogenated alkyl radical that contains at least one alpha-halogen atom of the group —COOH and has a total of two to ten carbon atoms.

6. The process according to claim 1 , in which all of said at least one olefinic effluent produced during the first oligomerization stage d) is sent directly into the second oligomerization stage e).

7. The process according to claim 1 , in which said at least one olefinic effluent that is produced during the first oligomerization stage d) undergoes at least one stage for treatment of said homogeneous catalyst and/or at least one stage for separation before being sent into the second oligomerization stage e).

8. The process according to claim 7 , in which said stage for treatment of said homogeneous catalyst is implemented by the use of collection mass or by treatment of the at least one olefinic effluent obtained from the first oligomerization stage d), neutralized or not, and that contains said homogeneous catalyst by an acid and/or a base.

9. The process according to claim 7 , in which said stage for treatment of said homogeneous catalyst is implemented by the separation of said at least one olefinic effluent obtained from the first oligomerization stage d), neutralized or not by a base, into a first effluent that comprises at least a portion of the olefinic compounds C9+ and also said homogeneous catalyst, and a second olefinic effluent that is free of said homogeneous catalyst, whereby said separation is followed by the treatment of the first effluent comprising at least a portion of the olefinic compounds C9+ and said homogeneous catalyst by acid and/or basic washing or by use of collection mass.

10. The process according to claim 7 , in which said separation stage is implemented between said stage for treatment of said homogeneous catalyst and the second oligomerization stage e), in such a way as to separate said at least one olefinic effluent obtained from the first oligomerization stage d) into at least one olefinic effluent that has four or more carbon atoms and at least one light olefinic effluent (C2-C4).

11. The process according to claim 10 , in which all of said C2-C4 light olefinic effluent is recycled to the first oligomerization stage d).

12. The process according to claim 1 , in which the second oligomerization stage e) is operated at a temperature of between 100 and 300° C., at a pressure of between 2 and 6 MPa, and at an hourly speed by weight of between 0.1 and 5 h −1 .

13. The process according to claim 1 , in which at least a portion of the kerosene hydrocarbon base obtained from fractionation stage f) undergoes a stage for hydrogenation of olefins that are produced from the oligomerization stages, wherein said hydrogenation is performed in the presence of a catalyst that comprises palladium or nickel, taken by themselves or in a mixture, and an alumina, silica, or silica-alumina substrate.

14. The process according to claim 13 , further comprising a separation stage following the hydrogenation stage to produce a kerosene fraction and/or a gas oil fraction and/or a fraction that has a boiling point that is higher than 360° C.

15. The process according to claim 1 , wherein the amorphous catalyst used in the second oligomerization stage e) comprises an amorphous mineral material selected from silica-aluminas and siliceous aluminas.

16. The process according to claim 1 , wherein the amorphous catalyst used in the second oligomerization stage e) is in the form of extrudates having a size of between 1 and 10 mm.

17. The process according to claim 1 , wherein dehydration stage b) is operated at a temperature of between 250 and 600° C, at an absolute pressure of between 0.1 and 5 MPa, and at an hourly speed by weight of between 0.1 and 50 h −1 .

18. The process according to claim 17 , wherein the dehydration stage b) is operated at a temperature of between 300 and 500° C, at an absolute pressure of between 0.1 and 1 MPa, and at an hourly speed by weight of between 0.5 and 15 h −1 .

19. The process according to claim 1 , wherein said effluent of dehydration stage b) comprises at least 97% by weight of ethylene relative to the total mass of the carbon compounds that are formed and present in said effluent.

20. The process according to claim 1 , wherein conversion of the purified ethanol feedstock in stage b) is greater than 90%.

21. The process according to claim 2 , wherein said at least one hydrocarbyl-aluminum halide is selected from dichloroethylaluminum, dichloroisobutylaluminum and dibromoethylaluminum, and said at least one Brönsted organic acid is

Assignees

• Guillon Emmanuelle
• Cadran Nicolas
• Touchais Natacha
• Bournay Laurent
• Magna Lionel
• Olivier-Bourbigou Helene
• IFP Energies Nouvelles

Inventors

• Guillon Emmanuelle
• Cadran Nicolas
• Touchais Natacha
• Bournay Laurent
• Magna Lionel
• Olivier-Bourbigou Helene

Classifications

• C10G2300/1014

  of vegetal origin · CPC title

• C10G2300/301

  Boiling range · CPC title

• Y02P30/20

  using bio-feedstock · CPC title

• C10G3/62

  Catalyst regeneration · CPC title

• C10G50/00 Primary

  Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation · CPC title